WO2022168631A1

WO2022168631A1 - Mixed composition

Info

Publication number: WO2022168631A1
Application number: PCT/JP2022/002095
Authority: WO
Inventors: 上原みちる大門; 友宏伊藤; 拓哉松浦
Original assignee: 住友化学株式会社
Priority date: 2021-02-05
Filing date: 2022-01-21
Publication date: 2022-08-11
Also published as: EP4289914A1; US20240018389A1; TW202242015A; KR20230142559A; JP2022120793A; CN116568773A

Abstract

The present invention is a mixed composition of solvent 1, solvent 2, and an organic silicon compound (C) having an amino group or an amine skeleton, wherein when the ratio of the hydrogen bond parameter (δH) and the dispersion parameter (δD) of Hansen solubility is δH/δD, the ratio (δH/δD) of solvent 1 is less than 0.410 and the ratio (δH/δD) of solvent 2 is 0.410 or greater.

Description

mixed composition

The present invention relates to a laminate including a mixed composition and an intermediate layer formed from the composition.

In various fields such as display devices such as touch panel displays, optical elements, semiconductor elements, building materials, window glass of automobiles and buildings, it is required to impart water repellency to the surface of the base material. Therefore, various water-repellent films are used as water-repellent coatings or water- and oil-repellent coatings.

A water-repellent film is usually used by being formed on a substrate, and when applying a composition for forming a water-repellent film to a substrate, it is necessary to form other layers such as a primer layer on the substrate in advance. , the composition may be applied to form a water-repellent coating or a water- and oil-repellent coating.

For example, in Patent Document 1, the surface of a cured coating film (I) having a glass transition temperature of 80 ° C. or higher is subjected to oxidation treatment, and then the treated surface is selected from isocyanate group-containing unsaturated compounds and isocyanate group-containing silane compounds. After forming the primer layer (II) by applying and drying the composition (A) containing at least one of the , that a functional layer such as water repellency can be formed on the surface of the cured coating film.

JP 2014-193988 A

Here, the appearance or properties of the primer layer composition may deteriorate during storage. Accordingly, an object of the present invention is to provide a composition having excellent storage stability.

The present invention, which has solved the above problems, is as follows.
[1] A mixed composition of an organosilicon compound (C) having an amino group or an amine skeleton, a solvent 1, and a solvent 2,
When the ratio of the hydrogen bonding term (δH) and the dispersion term (δD) in the Hansen solubility parameters is δH/δD, the ratio (δH/δD) of solvent 1 is less than 0.410, and the ratio of solvent 2 (δH /δD) is 0.410 or more.
[2] The composition according to [1], wherein the mass ratio of solvent 2 to solvent 1 is 0.01% by mass or more and 250% by mass or less.
[3] Solvent 2 has a Hansen solubility parameter distance Ra of 5 (J/cm ³ ) The composition according to [1] or [2] containing ^0.5 or less organic solvent 2-B.

[In the formula,
δD1: dispersion term (J/cm ³ ) of the Hansen solubility parameter of the organosilicon compound (C) ^0.5 ,
δD2: dispersion term of Hansen solubility parameter of organic solvent 2-B (J/cm ³ ) ^0.5 ,
δP1: the polar term of the Hansen solubility parameter of the organosilicon compound (C) (J/cm ³ ) ^0.5 ,
δP2: Polar term of Hansen solubility parameter of organic solvent 2-B (J/cm ³ ) ^0.5 ,
δH1: hydrogen bond term (J/cm ³ ) of the Hansen solubility parameter of the organosilicon compound (C) ^0.5 ,
δH2: Hydrogen bond term (J/cm ³ ) of Hansen solubility parameter of organic solvent 2-B is ^0.5 ]
[4] The composition according to [3], wherein the solvent 2 comprises a non-fluorinated alcoholic solvent 2-A and an organic solvent 2-B.
[5] The composition according to any one of [1] to [4], wherein solvent 1 is an ester solvent.
[6] The composition according to any one of [1] to [5], wherein a hydrolyzable group or a hydroxy group is bonded to at least one silicon atom in the organosilicon compound (C).
[7] The composition according to any one of [1] to [6], wherein the organosilicon compound (C) is a compound represented by any one of formulas (c1) to (c3).

In the above formula (c1),
R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple R ^x11 , the multiple R ^x11 may be different. may be different when there are a plurality of R ^x12 ; when there are a plurality of R ^x13 , a plurality of R ^x13 may be ^different ^; may be different from each other in a plurality of R ^x14 ,
Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^x11 are present; When there is a plurality of Rf x11, the plurality of Rf ^x11 may be different, when there are a plurality of Rf ^x12 , the plurality of Rf ^x12 may be different, and when there is a plurality of Rf ^x13 , the plurality of Rf ^x13 may be different. may be different, and if there are a plurality of Rf ^x14 , the plurality of Rf ^x14 may be different,
R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x15 are present, the plurality of R ^x15 may be different,
X ¹¹ is a hydrolyzable group, and when a plurality of X ¹¹ are present, the plurality of X ¹¹ may be different,
Y ¹¹ is -NH- or -S-, and when a plurality of Y ¹¹ are present, the plurality of Y ¹¹ may be different,
Z ¹¹ is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group;
p1 is an integer of 1 to 20, p2, p3, and p4 are each independently an integer of 0 to 10, p5 is an integer of 0 to 10,
p6 is an integer from 1 to 3,
has at least one Y ¹¹ which is —NH— when Z ¹¹ is not an amino group; when all Y ¹¹ are —S— or when p5 is 0, Z ¹¹ is an amino group;
Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 , p1 -{C(R ^x11 )(R ^x12 )}-units (U _c11 ), p2 -{C(Rf ^x11 ) (Rf ^x12 )}-unit (U _c12 ), p3-{Si (R ^x13 ) (R ^x14 )}-unit (U _c13 ), p4-{Si (Rf ^x13 )(Rf ^x14 )} The - unit (U _c14 ) and p5 -Y ¹¹ - units (U _c15 ) form one end of the compound represented by the formula (c1) where Z ¹¹ - is, and -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 is the other terminal, and the respective units (U _c11 ) to (U _c15 ) are aligned and bonded in any order unless —O— is linked to —O—.

In the above formula (c2),
R ^x20 and R ^x21 ^are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon ^atoms ^; When a plurality of R x21 are present, the plurality of R ^x21 may be different,
Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to ²⁰ carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom; ^x20 may be different, and when there are multiple Rf ^x21 , multiple Rf ^x21 may be different,
R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x22 and R ^x23 are present, a plurality of R ^x22 and R ^x23 may be different,
X ²⁰ and X ²¹ are each independently a hydrolyzable group, and when multiple X ²⁰ and X ²¹ are present, multiple X ²⁰ and X ²¹ may be different,
p20 is each independently an integer of 1 to 30, p21 is each independently an integer of 0 to 30, and at least one of the repeating units bracketed with p20 or p21 is an amine skeleton —NR ¹⁰⁰ —, wherein R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group;
p22 and p23 are each independently an integer of 1 to 3,
p20-{C( ^Rx20 )( ^Rx21 )}-units ( _Uc21 ), p21-{C( ^Rfx20 )( ^Rfx21 )}-units ( _Uc22 ) are p20 units ( U _c21 ) or p21 units (U _c22 ) do not need to be consecutive, and each unit (U _c21 ) and unit (U _c22 ) are lined up in any order and combined to form the formula (c2) One end of the compound is -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and the other end is -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

In the above formula (c3),
Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^x31 are present, the plurality of R ^x31 are different from each other. may be different when there ^{are a plurality of R x32} ^, and when there are a plurality of R ^x33 , a plurality of R ^x33 may be different ^; may be different from each other in a plurality of R ^x34 ,
Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^x31 are present; When there is a plurality of Rf x31, the plurality of Rf ^x31 may be different, when there are a plurality of Rf ^x32 , the plurality of Rf ^x32 may be different, and when there is a plurality of Rf ^x33 , the plurality of Rf ^x33 may be different. may be different, and if there are a plurality of Rf ^x34 , the plurality of Rf ^x34 may be different,
Y ³¹ is —NH—, —N(CH ₃ )— or —O—, and when there are a plurality of Y ³¹ , the plurality of Y ³¹ may be different,
X ³¹ , X ³² , X ³³ and X ³⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or aminoC _1-3 alkyldiC _1-3 alkoxysilyl is a group), and when a plurality of X ³¹ are present, the plurality of X ³¹ may be different, when a plurality of X ³² are present, the plurality of X ³² may be different, and X ³³ is When a plurality of X 33 are present, the plurality of X ³³ may be different, and when a plurality of X ³⁴ are present, the plurality of X ³⁴ may be different,
p31 is an integer of 0 to 20, p32, p33, and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, and p36 is an integer of 1 to 10 and p37 is 0 or 1,
at least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ is -NH- or -N(CH ₃ )-, and a compound represented by formula (c3) p31 -{C(R ^x31 )(R ^x32 )}-units, unless one end of is Z ³¹ - and the other end is Z ³² -, and -O- is not linked to -O- (U _c31 ), p32-{C(Rf ^x31 )(Rf ^x32 )}-units (U _c32 ), p33-{Si(R ^x33 )(R ^x34 )}-units (U _c33 ), p34 -{Si (Rf ^x33 ) (Rf ^x34 )}-units (U _c34 ), p 35 -Y ³¹ -units (U _c35 ), p 36 -{Si (X ³¹ ) (X ³² )-O }-unit (U _c36 ) and p37 -{Si(X ³³ )(X ³⁴ )}-units (U _c37 ) are arranged in arbitrary order and bonded together.
[8] The composition according to any one of [1] to [7], wherein the content of the organosilicon compound (C) is 0.005% by mass or more and 5% by mass or less.
[9] A laminate in which a substrate (s) and a water-repellent layer (r) are laminated via an intermediate layer (c),
A laminate, wherein the intermediate layer (c) is a layer formed from the composition according to any one of [1] to [8].
[10] The laminate according to [9], wherein the substrate (s) is composed of an organic material.
[11] A window film or touch panel display comprising the laminate according to [9] or [10].

According to the present invention, a composition with excellent storage stability can be provided.

<Composition>
The composition of the present invention is a mixed composition of an organosilicon compound (C) having an amino group or an amine skeleton, solvent 1, and solvent 2, wherein the hydrogen bonding term (δH) and the dispersion term ( δD) is defined as δH/δD, the ratio (δH/δD) of solvent 1 is less than 0.410, and the ratio (δH/δD) of solvent 2 is 0.410 or more. do. In addition, after mixing the said component, the thing which reacted during storage, for example is included in this invention. The organosilicon compound (C), solvent 1, and solvent 2 are described in order below.

1. Organosilicon compound (C)
Organosilicon compound (C) is an organosilicon compound having an amino group or an amine skeleton. By mixing the organosilicon compound (C) with the composition of the present invention, the intermediate layer (c) formed from the composition functions as a primer layer for the water-repellent layer (r) in the later-described laminate. can do. Therefore, in the laminate described later, the adhesion of the water-repellent layer (r) to the substrate (s) is improved, and as a result, the abrasion resistance of the laminate can be improved.

The organosilicon compound (C) mixed in the composition of the present invention may be one kind, or two or more kinds. As the organosilicon compound (C), one having at least one amine skeleton is preferred. The amine skeleton is represented by -NR ¹⁰ -, where R ¹⁰ is hydrogen or an alkyl group. R ¹⁰ is preferably hydrogen or an alkyl group having 1 to 5 carbon atoms. Moreover, when the organosilicon compound (C) contains a plurality of amine skeletons, the plurality of amine skeletons may be the same or different.

A hydrolyzable group or a hydroxy group is preferably bonded to at least one silicon atom in the organosilicon compound (C). Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group and an isocyanate group. Preferably, an alkoxy group having 1 to 4 carbon atoms or a hydroxy group is bonded to the silicon atom of the organosilicon compound (C).

The organosilicon compound (C) is preferably a compound represented by any one of the following formulas (c1) to (c3).

1-1. Organosilicon compound (C) represented by the following formula (c1) (hereinafter, organosilicon compound (C1))

In the above formula (c1),
R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^x11 are present, the plurality of R ^x11 are different from each other. may be different when there are a plurality of R ^x12 , and when there are a plurality of R ^x13 , a plurality of R ^x13 may be ^different ^; may be different from each other in a plurality of R ^x14 ,
Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^x11 are present; When there is a plurality of Rf x11, the plurality of Rf ^x11 may be different, when there are a plurality of Rf ^x12 , the plurality of Rf ^x12 may be different, and when there is a plurality of Rf ^x13 , the plurality of Rf ^x13 may be different. may be different, and if there are a plurality of Rf ^x14 , the plurality of Rf ^x14 may be different,
R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x15 are present, the plurality of R ^x15 may be different,
X ¹¹ is a hydrolyzable group, and when a plurality of X ¹¹ are present, the plurality of X ¹¹ may be different,
Y ¹¹ is -NH- or -S-, and when a plurality of Y ¹¹ are present, the plurality of Y ¹¹ may be different,
Z ¹¹ is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group;
p1 is an integer of 1 to 20, p2, p3, and p4 are each independently an integer of 0 to 10, p5 is an integer of 0 to 10,
p6 is an integer from 1 to 3,
has at least one Y ¹¹ which is —NH— when Z ¹¹ is not an amino group; when all Y ¹¹ are —S— or when p5 is 0, Z ¹¹ is an amino group;
Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 , p1 -{C(R ^x11 )(R ^x12 )}-unit (U _c11 ), p2 -{C(Rf ^x11 ) (Rf ^x12 )}-unit (U _c12 ), p3-{Si (R ^x13 ) (R ^x14 )}-unit (U _c13 ), p4-{Si (Rf ^x13 )(Rf ^x14 )} The - unit (U _c14 ) and p5 -Y ¹¹ - units (U _c15 ) form one end of the compound represented by the formula (c1) where Z ¹¹ - is, and -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 is the other end, and the respective units (U _c11 ) to (U _c15 ) are aligned and bonded in any order unless —O— is linked to —O—.

R ^x11 , R ^x12 , R ^x13 and R ^x14 are preferably hydrogen atoms.

Rf ^x11 , Rf ^x12 , Rf ^x13 and Rf ^x14 are each independently preferably an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom.

R ^x15 is preferably an alkyl group having 1 to 5 carbon atoms.

X ¹¹ is preferably an alkoxy group, a halogen atom, a cyano group or an isocyanate group, more preferably an alkoxy group, still more preferably an alkoxy group having 1 to 4 carbon atoms, a methoxy group or an ethoxy is particularly preferred.

Y ¹¹ is preferably -NH-.

Z ¹¹ is preferably a methacryloyl group, an acryloyl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, particularly preferably an amino group.

p1 is preferably 1-15, more preferably 2-10. Each of p2, p3 and p4 is independently preferably 0-5, more preferably 0-2. p5 is preferably 0-5, more preferably 0-3, still more preferably 1-3. p6 is preferably 2 to 3, more preferably 3.

As the organosilicon compound (C), in the above formula (c1), both R ^x11 and R ^x12 are hydrogen atoms, Y ¹¹ is —NH—, and X ¹¹ is an alkoxy group (especially a methoxy group or an ethoxy group ), Z ¹¹ is an amino group or a mercapto group, p1 is 1 to 10, p2, p3 and p4 are all 0, p5 is 0 to 5 (especially 1 to 3), p6 is preferably 3.

Note that the p1 units (U _c11 ) _do not need to be continuously bonded to each other, and may be bonded via other units in the middle. Just do it. The same applies to the units (U _c12 ) to (U _c15 ) bounded by p2 to p5.

The organosilicon compound (C1) is preferably represented by the following formula (c1-2).

In the above formula (c1-2),
X ¹² is a hydrolyzable group, and when a plurality of X ¹² are present, the plurality of X ¹² may be different,
Y ¹² is -NH-,
Z ¹² is an amino group or a mercapto group,
R ^x16 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x16 are present, the plurality of R ^x16 may be different,
p is an integer of 1 to 3, q is an integer of 2 to 5, r is an integer of 0 to 5, s is 0 or 1,
When s is 0, Z ¹² is an amino group.

X ¹² is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, still more preferably an alkoxy group having 1 to 4 carbon atoms, a methoxy group or An ethoxy group is particularly preferred.

Z ¹² is preferably an amino group.

R ^x16 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

p is preferably an integer of 2 to 3, more preferably 3.

When s is 1, q is preferably an integer of 2 to 3, r is preferably an integer of 2 to 4, and when s is 0, the sum of q and r is 1 to 5. Preferably.

1-2. Organosilicon compound (C) represented by the following formula (c2) (hereinafter, organosilicon compound (C2))

In the above formula (c2),
R ^x20 and R ^x21 ^are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon ^atoms ^; When a plurality of R x21 are present, the plurality of R ^x21 may be different,
Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to ²⁰ carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom; ^x20 may be different, and when there are multiple Rf ^x21 , multiple Rf ^x21 may be different,
R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x22 and R ^x23 are present, a plurality of R ^x22 and R ^x23 may be different,
X ²⁰ and X ²¹ are each independently a hydrolyzable group, and when multiple X ²⁰ and X ²¹ are present, multiple X ²⁰ and X ²¹ may be different,
p20 is an integer of ¹ to 30; p21 is an integer of 0 to 30; and R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group,
p22 and p23 are each independently an integer of 1 to 3,
p20-{C( ^Rx20 )( ^Rx21 )}-units ( _Uc21 ), p21-{C( ^Rfx20 )( ^Rfx21 )}-units ( _Uc22 ) are p20 units ( U _c21 ) or p21 units (U _c22 ) do not need to be consecutive, and each unit (U _c21 ) and unit (U _c22 ) are lined up in any order and combined to form the formula (c2) One end of the compound is -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and the other end is -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

R ^x20 and R ^x21 are preferably hydrogen atoms.

Rf ^x20 and Rf ^x21 are each independently preferably an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom.

R ^x22 and R ^x23 are preferably C 1-5 alkyl groups.

X ²⁰ and X ²¹ are preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, even more preferably an alkoxy group having 1 to 4 carbon atoms, methoxy or ethoxy groups are particularly preferred.

As described above, at least one amine skeleton —NR ¹⁰⁰ — may be present in the molecule, and the amine skeleton may be replaced by either a repeating unit bracketed with p20 or p21. , p20 are preferably part of a bracketed repeating unit. A plurality of the amine skeletons may be present, and in that case, the number of amine skeletons is preferably 1-10, more preferably 1-5, and even more preferably 2-5. In this case, it is preferable to have -{C(R ^x20 )(R ^x21 )} _p200 - between adjacent amine skeletons, and p200 is preferably 1 to 10, preferably 1 to 5. is more preferred. p200 is included in the total number of p20s.

In the amine skeleton —NR ¹⁰⁰ —, when R ¹⁰⁰ is an alkyl group, the number of carbon atoms is preferably 5 or less, more preferably 3 or less. The amine skeleton -NR ¹⁰⁰ - is preferably -NH- (R ¹⁰⁰ is a hydrogen atom).

p20 is preferably 1-15, more preferably 1-10, excluding the number of repeating units replaced by the amine skeleton.

p21 is preferably 0 to 5, more preferably 0 to 2, excluding the number of repeating units replaced by the amine skeleton.

p22 and p23 are preferably 2 to 3, more preferably 3.

As the organosilicon compound (C2), in the above formula (c2), R ^x20 and R ^x21 are both hydrogen atoms, X ²⁰ and X ²¹ are alkoxy groups (especially methoxy groups or ethoxy groups), and p20 is and at least one repeating unit enclosed in parentheses is replaced with an amine skeleton —NR ¹⁰⁰ —, R ¹⁰⁰ is a hydrogen atom, and p20 is 1 to 10 (provided that the amine skeleton is substituted excluding the number of repeating units), it is preferable to use a compound in which p21 is 0 and p22 and p23 are 3.

Incidentally, the reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP-A-2012-197330, which is used as compound (C) in the examples described later ( Product name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) is represented by the above formula (c2), where R ^x20 and R ^x21 are both hydrogen atoms, and p20 is 8 (however, it is replaced by an amine skeleton excluding the number of repeating units), p21 is 0, two amine skeletons (both R ¹⁰⁰ are hydrogen atoms), both terminals are the same, p22 and p23 are 3, and X ²⁰ and X ²¹ are methoxy groups.

The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).

In the above formula (c2-2),
X ²² and X ²³ are each independently a hydrolyzable group, and when a plurality of X ²² and X ²³ are present, the plurality of X ²² and X ²³ may be different,
R ^x24 and R ^x25 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x24 and R ^x25 are present, a plurality of R ^x24 and R ^x25 may be different,
—C _w H _2w — has at least one of its methylene groups replaced with an amine skeleton —NR ¹⁰⁰ —, where R ¹⁰⁰ is a hydrogen atom or an alkyl group;
w is an integer of 1 to 30 (excluding the number of methylene groups substituted for the amine skeleton),
p24 and p25 are each independently an integer of 1-3.

X ²² and X ²³ are preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, even more preferably an alkoxy group having 1 to 4 carbon atoms, methoxy or ethoxy groups are particularly preferred.

A plurality of amine skeletons —NR ¹⁰⁰ — may be present, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and more preferably 2 to 5. More preferred. Moreover, in this case, it is preferable to have an alkylene group between adjacent amine skeletons. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The number of carbon atoms in the alkylene groups between adjacent amine skeletons is included in the total number of w.

R ^x24 and R ^x25 are preferably alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 5 carbon atoms.

p24 and p25 are preferably integers of 2 to 3, more preferably 3.

w is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 10 or less.

1-3. Organosilicon compound (C) represented by the following formula (c3) (hereinafter, organosilicon compound (C3))

In the above formula (c3),
Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group. Reactive functional groups include vinyl, α-methylvinyl, styryl, methacryloyl, acryloyl, amino, epoxy, ureido, or mercapto groups. Z ³¹ and Z ³² are preferably an amino group, a mercapto group, or a methacryloyl group, particularly preferably an amino group.

R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^x31 are present, the plurality of R ^x31 are different from each other. may be different when there ^{are a plurality of R x32} ^, and when there are a plurality of R ^x33 , a plurality of R ^x33 may be different ^; may be different from each other in a plurality of R ^x34 . R ^x31 , R ^x32 , R ^x33 and R ^x34 are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom.

Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^x31 are present; When there is a plurality of Rf x31, the plurality of Rf ^x31 may be different, when there are a plurality of Rf ^x32 , the plurality of Rf ^x32 may be different, and when there is a plurality of Rf ^x33 , the plurality of Rf ^x33 may be different. When there are a plurality of Rf ^x34 , the plurality of Rf ^x34 may be different. Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are preferably C 1-10 alkyl groups in which one or more hydrogen atoms are substituted with fluorine atoms or fluorine atoms.

Y ³¹ is —NH—, —N(CH ₃ )— or —O—, and when there are multiple Y ³¹ s, the multiple Y ^31s may be different. Y ³¹ is preferably -NH-.

X ³¹ , X ³² , X ³³ and X ³⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or aminoC _1-3 alkyldiC _1-3 alkoxysilyl is a group), and when a plurality of X ³¹ are present, the plurality of X ³¹ may be different, when a plurality of X ³² are present, the plurality of X ³² may be different, and X ³³ is When a plurality of X 33 are present, the plurality of X ³³ may be different, and when a plurality of X ³⁴ are present, the plurality of X ³⁴ may be different. X ³¹ , X ³² , X ³³ and X ³⁴ are preferably —OR ^c in which R ^c is a hydrogen atom ^or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom.

p31 is an integer of 0 to 20, p32, p33, and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, and p36 is an integer of 1 to 10 and p37 is 0 or 1. p31 is preferably 1-15, more preferably 3-13, still more preferably 5-10. p32, p33 and p34 are each independently preferably 0-5, more preferably 0-2. p35 is preferably 0-3. p36 is preferably 1-5, more preferably 1-3. p37 is preferably 1.

The organosilicon compound (C3) satisfies the condition that at least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ is —NH— or —N(CH ₃ )—, and the formula ^p31 ^- {C(R ^x31 ) (R ^x32 )}-unit (U _c31 ), p32-{C(Rf ^x31 )(Rf ^x32 )}-unit (U _c32 ), p33-{Si(R ^x33 )(R ^x34 )} - unit (U _c33 ), p34 -{Si(Rf ^x33 )(Rf ^x34 )} - unit (U _c34 ), p35 -Y ³¹ - unit (U _c35 ), p36 -{Si(X ³¹ ) (X ³² )-O}-unit (U _c36 ) and p37 -{Si(X ³³ )(X ³⁴ )}-units (U _c37 ) arranged in arbitrary order and bonded together be. The p31 units (U _c31 ) do not need to be continuously linked, _and may be linked via other units in the middle, and the total number of p31 units may be p31. . The same applies to the units (U _c32 ) to (U _c37 ) enclosed by p32 to p37.

As the organosilicon compound (C3), Z ³¹ and Z ³² are amino groups, R ^x31 and R ^x32 are hydrogen atoms, p31 is 3 to 13 (preferably 5 to 10), and R ^x33 and R all of ^x34 are hydrogen atoms, all of Rf ^x31 to Rf ^x34 are alkyl groups having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or fluorine atoms, and p32 to p34 are all 0 to 5, Y ³¹ is —NH—, p35 is 0 to 5 (preferably 0 to 3), X ³¹ to X ³⁴ are all —OH, and p36 is 1 to 5 (preferably is 1-3) and p37 is 1 is preferred.

The organosilicon compound (C3) is preferably represented by the following formula (c3-2).

In formula (c3-2), Z ³¹ , Z ³² , X ³¹ , X ³² , X ³³ , X ³⁴ and Y ³¹ have the same meanings as those in formula (c3), and p41 to p44 are each independent is an integer of 1 to 6, and p45 and p46 are each independently 0 or 1.

In formula (c3-2), Z ³¹ and Z ³² are preferably an amino group, a mercapto group or a methacryloyl group, particularly preferably an amino group. X ³¹ , X ³² , X ³³ and X ³⁴ are preferably —OR ^c in which R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably R ^c is a hydrogen atom . Y ³¹ is preferably -NH-. p41 to p44 are preferably 1 or more, preferably 5 or less, and more preferably 4 or less. Both p45 and p46 are preferably 0.

The composition of the present invention is a composition in which the organosilicon compound (C) and solvents 1 and 2 described later are mixed. The composition of the present invention is obtained by mixing the organosilicon compound (C), solvent 1 and solvent 2, and when components other than the above components are mixed, the organosilicon compound (C), solvent 1 and It is obtained by mixing solvent 2 with other components. The composition of the present invention includes those that have undergone a reaction after mixing, for example, during storage. For example, it includes a compound whose hydrolyzable group is a —SiOH group by hydrolysis. Further, as an example of the progress of the reaction during storage of the composition, the composition may contain a condensate of the organosilicon compound (C). The —SiOH group of C) or the —SiOH group of the organosilicon compound (C) generated by hydrolysis undergoes dehydration condensation with —SiOH groups derived from the organosilicon compound (C) or —SiOH groups derived from other compounds. and condensates formed by More specifically, the condensate includes, for example, an organosilicon compound (C3') in which the organosilicon compound (C3) is condensed with at least one of X ³¹ to X ³⁴ and bonded.

The organosilicon compound (C3′) has two or more structures (c31-1) represented by the following formula (c31-1), and the structures (c31-1) are represented by *3 or *4 below. A chain or ring-bonded compound, wherein the bond in *3 or *4 below is due to the condensation of two or more of the organosilicon compounds (C3) above X ³¹ or X ³² ,
*1 and *2 in the following formula (c31-1) are, respectively, at least the units enclosed by p31, p32, p33, p34, p35, (p36)-1, and p37 in the following formula (c31-2) One type is bonded in any order and a group having a terminal Z- is bonded, and the groups bonded to *1 and *2 may be different for each of the plurality of structures (c31-1),
When a plurality of structures (c31-1) are bonded in a chain, *3, which is the terminal, is a hydrogen atom, and *4 is a hydroxy group.

In the formula (c31-2),
Z is a reactive functional group other than a hydrolyzable group and a hydroxy group;
R ^x31 , R ^x32 , R ^x33 , R ^x34 , Rf ^x31 , Rf ^x32 , Rf ^x33 , Rf ^x34 , Y ³¹ , X ³¹ , X ³² , X ³³ , X ³⁴ , p31 to p37 are are synonymous with these signs of

When the organosilicon compound (C3) is a compound represented by the above formula (c3-2), the organosilicon compound (C3′) is, for example, a structure represented by the following formula (c31-3) *3 below. or *4 may be a chain or ring-bonded compound. When the structure represented by the following formula (c31-3) is linked in a chain, the terminal *3 is a hydrogen atom and the terminal *4 is a hydroxy group.

All the symbols in the above formula (c31-3) have the same meanings as the symbols in the above formula (c3-2).

The organosilicon compound (C3') is preferably a compound in which 2 to 10 (preferably 3 to 8) structures represented by the formula (c31-3) are bonded.

As the organosilicon compound (C), only one type may be used, or two or more types may be used. As the organosilicon compound (C), it is preferable to use at least the organosilicon compound (C1) and/or the organosilicon compound (C2).

The total amount of the organosilicon compound (C) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, when the entire composition of the present invention is 100% by mass. It is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass. or less, more preferably 2% by mass or less. The amount of the above organosilicon compound (C) can be adjusted during preparation of the composition. The amount of the organosilicon compound (C) may be calculated from the analysis results of the composition. As a method of specifying from the analysis results of the composition, for example, the type of each compound contained in the composition is analyzed by gas chromatography mass spectrometry, liquid chromatography mass spectrometry, etc., and the obtained analysis The results can be identified by library searching, and the amount of each compound contained in the composition can be calculated from the above analytical results using the calibration curve method. In addition, in the present specification, when the range of the amount or mass ratio of each component is described, the range can be adjusted at the time of preparation of the composition.

2. Solvent 1
The Hansen solubility parameter divides the solubility parameter introduced by Hildebrand into three components: the dispersion term (δD), the polar term (δP), and the hydrogen bonding term (δH). It is represented. The dispersion term (δD) indicates the effect of the dispersion force, the polar term (δP) indicates the effect of the dipole force, and the hydrogen bond term (δH) indicates the effect of the hydrogen bond force.

The definition and calculation of the Hansen Solubility Parameters are described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007). In addition, by using the computer software Hansen Solubility Parameters in Practice (HSPiP), the Hansen Solubility Parameters can be easily estimated from the chemical structure of compounds for which literature values are not known. Furthermore, for compounds for which literature values are unknown, it is possible to calculate the Hansen solubility parameter by using the melting sphere method described later. In the present invention, when determining the Hansen Solubility Parameters of solvents, HSPiP version 5.2.05 is used to use registered Hansen Solubility Parameter values for solvents registered in the database, and Regarding, the Hansen solubility parameter is calculated by using the melting sphere method described later.

The dissolving sphere method is a method for calculating the Hansen solubility parameter of a target substance, in which the target substance is dissolved or dispersed in many different solvents whose Hansen solubility parameters It can be determined by a solubility test that evaluates solubility or dispersibility. The type of solvent used in the solubility test is preferably selected so that the total value of the HSP dispersion term, polar term and hydrogen bonding term of each solvent varies widely between solvents, more specifically, preferably It is preferable to evaluate using 10 or more solvents, more preferably 15 or more solvents, and still more preferably 17 or more solvents. Specifically, among the solvents used in the solubility test, all the three-dimensional points of the solvent that dissolved or dispersed the target substance were included inside the sphere, and the points of the solvent that did not dissolve or disperse were outside the sphere. A sphere (solubility sphere) having the smallest radius is searched for, and the center coordinates of the sphere are used as the Hansen solubility parameter of the object. Evaluation of solubility and dispersibility is carried out by visually determining whether or not the target substance is dissolved in the solvent and whether or not it is dispersed. If the mixture of the target substance and the solvent becomes cloudy, the target substance precipitates, or the target substance and the solvent separate into layers, it can be determined that the target substance is not dissolved or dispersed in the solvent. A specific method for the solubility test will be described in detail in the Examples section.

For example, if the Hansen Solubility Parameters of some other solvent that was not used to determine the Hansen Solubility Parameters of the object was (δd, δp, δh), then the point indicated by the coordinates would be inside the solubility sphere of the object. , the solvent is believed to dissolve or disperse the object. On the other hand, if the coordinate point is outside the solubility sphere of the target, the solvent is considered incapable of dissolving or dispersing the target.

In the present invention, in the Hansen solubility parameters of solvents, when the ratio of the hydrogen bonding term (δH) and the dispersion term (δD) is δH/δD, the ratio (δH/δD) is less than 0.410. called. By including the solvent 1 in the composition of the present invention, the coatability is improved and the appearance of the laminated body is improved. In this specification, the solvent refers to a compound that is liquid at room temperature.

Solvent 1 is a solvent mixture consisting of two or more compounds each having a ratio (δH/δD) of less than 0.410, even if it is a single solvent comprising a compound having a ratio (δH/δD) of less than 0.410. may be either. The ratio (δH/δD) of the compounds contained in the solvent 1 is preferably 0.400 or less, may be 0.10 or more, preferably 0.20 or more, and more preferably 0.30 or more. be.

Examples of the solvent 1 include ester solvents 1-A such as butyl acetate and butyl benzoate; ketone solvents 1-A such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; ether solvents such as diethyl ether. Solvent 1-A: Hydrocarbon solvent 1-A such as benzene, toluene, xylene, pentane, hexane, cyclohexane, etc.; Among them, ester solvent 1-A is preferred, and butyl acetate is particularly preferred. The ester solvent 1-A, the ketone solvent 1-A, the ether solvent 1-A, and the hydrocarbon solvent 1-A each have a ratio (δH/δD) of less than 0.410. Refers to solvents, ketone solvents, ether solvents, and hydrocarbon solvents.

From the viewpoint of coatability, the amount of solvent 1 is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, and still more preferably 100% by mass of the composition of the present invention. It is 90% by mass or more, more preferably 98% by mass or more, and may be 99.9% by mass or less.

The content of solvent 1 with respect to 1 part by mass of the organosilicon compound (C) is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 100 parts by mass or more, from the viewpoint of improving coatability. More preferably 150 parts by mass or more, particularly preferably 300 parts by mass or more, and from the viewpoint of further improving the storage stability of the composition, it is preferably 20000 parts by mass or less, more preferably 10000 parts by mass. Below, it is more preferably 1000 parts by mass or less, more preferably 600 parts by mass or less, and particularly preferably 500 parts by mass or less.

3. Solvent 2
Solvent 2 is a solvent composed of a compound having the above ratio (δH/δD) of 0.410 or more. By including the solvent 2 together with the solvent 1 in the composition of the present invention, a composition with good storage stability can be obtained, and preferably a composition with good storage stability and coatability can be obtained. . As described above, in a preferred embodiment, a hydrolyzable group or a hydroxy group is bonded to the silicon atom of the organosilicon compound (C), and during storage of the composition, the —SiOH group possessed by the organosilicon compound (C) Alternatively, the progress of the condensation reaction between the —SiOH groups of the organosilicon compound (C) generated by the hydrolysis of the hydrolyzable groups bonded to the silicon atoms is one of the factors that reduce the storage stability of the composition. It is considered. However, since the composition of the present invention contains the solvent 2 together with the solvent 1, such a condensation reaction and the like can be suppressed. The storage stability of the composition can be evaluated, for example, by measuring the number of days until the composition becomes cloudy after preparation. For example, when the composition of the present invention is placed in an atmosphere with a temperature of 22° C. and a relative humidity of 55%, the number of days until white turbidity is observed is, for example, 2 days or more, preferably 5 days or more, more preferably 5 days or more. It is 8 days or more, more preferably 10 days or more, and for example 200 days or less.

Solvent 2 is a solvent mixture consisting of two or more compounds each having a ratio (δH/δD) of 0.410 or more, even if it is a single solvent comprising a compound having a ratio (δH/δD) of 0.410 or more. may be either. The ratio (δH/δD) of the compounds contained in the solvent 2 is preferably 0.430 or more, and may be 1.8 or less, preferably 1.5 or less, more preferably 1.3 or less. be.

Specific examples of the solvent 2 include non-fluorine-type solvents such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, n-amyl alcohol, diacetone alcohol, and benzyl alcohol. Alcohol-based solvent 2-A; 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol, perfluorooctylethanol, 1,1,3,3 ,3-hexafluoro-2-propanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1-nonaol, 1H,1H,2H,2H-tridecafluoro- Fluorine-containing alcohol solvent 2-A such as 1-n-octanol, 1H, 1H, 2H, 2H-nonafluoro-1-hexanol; Ketone solvent 2-A such as acetone; Ether solvent 2-A such as tetrahydrofuran Ether alcohol solvent 2-A such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene glycol; Ether ester solvent 2-A such as propylene glycol monomethyl ether acetate and ethylene glycol monobutyl ether acetate; be done. In this specification, non-fluorinated alcohol solvent 2-A, fluorine-containing alcohol solvent 2-A, ketone solvent 2-A, ether solvent 2-A, ether alcohol solvent 2-A, and The ether ester solvent 2-A is a non-fluorinated alcohol solvent, a fluorine-containing alcohol solvent, a ketone solvent, an ether solvent, and an ether alcohol solvent, each having a ratio (δH/δD) of 0.410 or more. , and refers to ether ester solvents. Further, in this specification, the term "non-fluorinated alcoholic solvent" refers to an alcoholic solvent having no fluorine atoms, and the term "fluorine-containing alcoholic solvent" refers to an alcoholic solvent having at least one fluorine atom. Ketone solvents do not include solvents having alcoholic hydroxyl groups.

As the solvent 2, a non-fluorinated alcoholic solvent 2-A or a distance Ra of the Hansen solubility parameter to the organosilicon compound (C) calculated based on the formula (E.1) is 5 (J/cm ³ ). It preferably contains ^0.5 or less organic solvent 2-B, and may be a mixed solvent containing non-fluorinated alcohol solvent 2-A and organic solvent 2-B.

Among non-fluorinated alcohol solvents 2-A, alkyl alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutyl alcohol, or alcoholic hydroxyl groups and diacetone alcohols in the molecule A keto alcohol having a carbonyl group is preferred, an alkyl alcohol having 1 to 3 carbon atoms or diacetone alcohol is more preferred, and ethanol or diacetone alcohol is particularly preferred.

From the viewpoint of improving the solubility of the organosilicon compound (C), the amount of the non-fluorinated alcoholic solvent 2-A is preferably 0.01% by mass or more, more preferably 0%, based on 100% by mass of the composition of the present invention. 0.03% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably It is 0.1% by mass or less.

Organic solvent 2-B is an organic solvent composed of a compound having a Hansen solubility parameter distance Ra of 5 (J/cm ³ ) ^0.5 or less from the organosilicon compound (C) calculated based on formula (E.1). be.

[In the formula,
δD1: dispersion term (J/cm ³ ) of the Hansen solubility parameter of the organosilicon compound (C) ^0.5 ,
δD2: dispersion term of Hansen solubility parameter of organic solvent 2-B (J/cm ³ ) ^0.5 ,
δP1: the polar term of the Hansen solubility parameter of the organosilicon compound (C) (J/cm ³ ) ^0.5 ,
δP2: Polar term of Hansen solubility parameter of organic solvent 2-B (J/cm ³ ) ^0.5 ,
δH1: hydrogen bond term (J/cm ³ ) of the Hansen solubility parameter of the organosilicon compound (C) ^0.5 ,
δH2: Hydrogen bonding term (J/cm ³ ) of Hansen solubility parameter of organic solvent 2-B is ^0.5 ]

The organic solvent 2-B has a ratio (δH/δD) of 0.410 or more and a distance Ra of 5 (J/cm ³ ) ^0.5 or less calculated based on the above formula (E.1). It is an organic solvent consisting of compounds. The organic solvent 2-B may be either a single solvent consisting of a compound satisfying the above conditions or a solvent mixture consisting of two or more compounds each satisfying the above conditions.

From the viewpoint of improving the solubility of the organosilicon compound (C), the compound contained in the organic solvent 2-B has a distance Ra calculated based on the above formula (E.1) of 4.8 (J/cm ³ ) is preferably ^0.5 or less, more preferably 4.0 (J/cm ³ ) ^0.5 or less, still more preferably 3.5 (J/cm ³ ) ^0.5 or less, and 0.5 (J/cm ³ ) It may be ^0.5 or more, 1.0 (J/cm ³ ) ^0.5 or more, or 2.0 (J/cm ³ ) ^0.5 or more.

In formula (E.1), the Hansen solubility parameter of the organosilicon compound (C) can use the value determined by the above-described dissolving sphere method. Also, when the organosilicon compound (C) is a mixture of two compounds, the Hansen solubility parameter of the organosilicon compound (C) can be calculated based on formula (E.2). Volume fractions can also be approximated to weight fractions. In formula (E.2), one of the above two compounds is described as an organosilicon compound (Cc1) and the other as an organosilicon compound (Cc2).

[In the formula, δD1, δP1, and δH1 are the same as in formula (E.1).
x _I is the volume fraction of the organosilicon compound (Cc1) in the organosilicon compound (C);
x _II is the volume fraction of the organosilicon compound (Cc2) in the organosilicon compound (C);
(δD1 ^I , δP1 ^I , δH1 ^I ) is the Hansen solubility parameter of the organosilicon compound (Cc1);
(δD1 ^II , δP1 ^II , δH1 ^II ) are the Hansen solubility parameters of the organosilicon compound (Cc2). ]

The Hansen solubility parameter of the organosilicon compound (C) can also be calculated by similar calculations when the organosilicon compound (C) is a mixture of three or more types.

Specific examples of the organic solvent 2-B may vary depending on the organosilicon compound (C), but are compounds with a distance Ra of 5 (J/cm ³ ) ^0.5 or less calculated based on the above formula (E.1). As long as the above non-fluorinated alcohol solvent 2-A, fluorine-containing alcohol solvent 2-A, ketone solvent 2-A, ether solvent 2-A, ether alcohol solvent 2-A, and ether ester solvent Compounds exemplified for solvent 2-A may also be used. When the solvent 2 contains the non-fluorinated alcohol solvent 2-A and the organic solvent 2-B, the organic solvent 2-B does not contain the non-fluorinated alcohol solvent 2-A.

The amount of the organic solvent 2-B is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and 75% by mass or less in 100% by mass of the composition of the present invention. It is preferably 20% by mass or less, still more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

The total amount of the non-fluorinated alcohol solvent 2-A and the organic solvent 2-B is preferably 50% by mass or more, more preferably 80% by mass or more, when the entire solvent 2 is 100% by mass. , more preferably 90% by mass or more, particularly preferably 98% by mass or more, and may be 100% by mass.

When the solvent 2 contains the non-fluorine alcohol solvent 2-A and the organic solvent 2-B, the amount of the non-fluorine alcohol solvent 2-A is the same as the non-fluorine alcohol solvent 2-A and the organic solvent 2. In the total 100% by mass of -B, it is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 50% by mass or less, more It is preferably 30% by mass or less, more preferably 20% by mass or less.

Further, the solvent 2 preferably contains at least a non-fluorine alcohol solvent 2-A, a fluorine-containing alcohol solvent 2-A, or a ketone solvent 2-A. More preferably, the fluorine-containing alcohol solvent 2-A, the ketone solvent 2-A, or a mixed solvent thereof.

In this case, as the non-fluorinated alcohol solvent 2-A, alkyl alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol and isobutyl alcohol, or keto alcohols such as diacetone alcohol are preferable. , more preferably alkyl alcohol or diacetone alcohol having 1 to 3 carbon atoms, and particularly preferably ethanol or diacetone alcohol.
The fluorine-containing alcoholic solvent 2-A is preferably an alkyl alcohol having 2 to 10 carbon atoms in which two or more hydrogen atoms are substituted with fluorine atoms, more preferably a perfluoroalkylene structure in the molecule. and particularly preferably 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol.
Further, the ketone-based solvent 2-A is preferably a ketone having an alkyl group bonded to both sides of the carbonyl group, more preferably a ketone having an alkyl group having 1 to 3 carbon atoms bonded to both sides of the carbonyl group. and particularly preferably acetone.

The amount of the non-fluorinated alcoholic solvent 2-A is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and 5% by mass or less in 100% by mass of the composition of the present invention. is preferred, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. The amount of non-fluorinated alcoholic solvent 2-A may be 75% by mass or less, or 0.1% by mass or less, based on 100% by mass of the composition of the present invention.
The amount of the fluorine-containing alcoholic solvent 2-A is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.10% by mass in 100% by mass of the composition of the present invention. % by mass or more, more preferably 0.15% by mass or more, preferably 20% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and still more preferably 0.5% by mass. It is below. The amount of fluorine-containing alcoholic solvent 2-A may be 75% by mass or less in 100% by mass of the composition of the present invention.
Further, the amount of ketone solvent 2-A is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.10% by mass or more in 100% by mass of the composition of the present invention. , more preferably 0.15% by mass or more, and preferably 75% by mass or less. The amount of ketone solvent 2-A is 20% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.5% by mass or less in 100% by mass of the composition of the present invention. good too.

The total amount of the non-fluorinated alcohol solvent 2-A, the fluorine-containing alcohol solvent 2-A, and the ketone solvent 2-A is 50% by mass or more when the total amount of the solvent 2 is 100% by mass. preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 98% by mass or more, and may be 100% by mass.

When the solvent 2 is a mixed solvent containing two or more solvents selected from the group consisting of the non-fluorinated alcohol solvent 2-A, the fluorine-containing alcohol solvent 2-A, and the ketone solvent 2-A, A mixed solvent containing the fluorinated alcohol solvent 2-A and the ketone solvent 2-A, or a mixed solvent containing the non-fluorinated alcohol solvent 2-A and the ketone solvent 2-A is preferable.

When the solvent 2 is a mixed solvent of the fluorine-containing alcohol solvent 2-A and the ketone solvent 2-A, the amount of the fluorine-containing alcohol solvent 2-A is equal to that of the fluorine-containing alcohol solvent 2-A. and the ketone-based solvent 2-A in a total of 100% by mass, preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and 50% by mass or less. is preferred, more preferably 30% by mass or less, and even more preferably 20% by mass or less. Further, when the solvent 2 is a mixed solvent of the non-fluorinated alcohol solvent 2-A and the ketone solvent 2-A, the amount of the non-fluorinated alcohol solvent 2-A is -A and ketone solvent 2-A in total 100% by mass, preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and 50% by mass or less is preferably 30% by mass or less, more preferably 20% by mass or less.

The amount of the solvent 2 is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and 75% by mass or less when the entire composition of the present invention is 100% by mass. Preferably. The amount of the solvent 2 when the entire composition of the present invention is 100% by mass may be 20% by mass or less, may be 5% by mass or less, or may be 1% by mass or less. .

The content of the solvent 2 relative to 1 part by mass of the organosilicon compound (C) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, and It is preferably 300 parts by mass or less. The content of the solvent 2 with respect to 1 part by mass of the organosilicon compound (C) may be 20 parts by mass or less, 10 parts by mass or less, or 3 parts by mass or less.

The total amount of solvent 1 and solvent 2 is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more when the entire composition of the present invention is 100% by mass. , more preferably 98% by mass or more, and may be 99.9% by mass or less.

The mass ratio of solvent 2 to solvent 1 is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and 250% by mass or less. is preferably By adjusting the mass ratio of Solvent 1 and Solvent 2 to the above range, the storage stability of the composition can be improved, and the appearance of the obtained laminate can be improved. The mass ratio of solvent 2 to solvent 1 may be 100% by mass or less, 20% by mass or less, or 5% by mass or less. Further, by setting the mass ratio of the solvent 2 to the solvent 1 to 0.2% by mass or more and 250% by mass or less, preferably 2% by mass or more and 250% by mass or less, the storage stability of the composition can be further improved. By setting the mass ratio of the solvent 2 to the solvent 1 to 0.1% by mass or less, preferably 0.05% by mass or less, the sliding angle of the resulting laminate can be made smaller.

The total amount of the organosilicon compound (C), the solvent 1 and the solvent 2 is preferably 90% by mass or more, more preferably 95% by mass or more, when the entire composition of the present invention is 100% by mass. , more preferably 98% by mass or more, and may be 100% by mass.

The composition of the present invention contains a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, an antiviral agent, and a biofouling agent, as long as the effects of the present invention are not impaired. Various additives such as inhibitors, deodorants, pigments, flame retardants, and antistatic agents may be mixed. The amount of the additive is preferably 5% by mass or less, more preferably 1% by mass or less, based on 100% by mass of the mixed composition of the present invention.

The composition of the present invention can be used as a coating agent for the intermediate layer between the substrate and the water-repellent layer. The composition of the present invention (hereinafter sometimes referred to as intermediate layer-forming composition) has excellent storage stability. Further, according to one aspect of the present invention, even if the laminate is obtained using the composition for forming an intermediate layer immediately after preparation, the laminate obtained using the composition for forming an intermediate layer after being stored after preparation Even in the body, the physical properties (preferably abrasion resistance) and/or appearance of the laminate remain good. A laminate including an intermediate layer formed from the intermediate layer-forming composition of the present invention will be described below.

<Laminate>
The laminate of the present invention is a laminate in which a substrate (s) and a water-repellent layer (r) are laminated via an intermediate layer (c), and the intermediate layer (c) is composed of the composition of the present invention. It is characterized by being a layer formed from an object. The laminate of the present invention has good water repellency, preferably good water repellency and abrasion resistance.

1. base material (s)
The material of the base material (s) is not particularly limited, and may be either an organic material or an inorganic material, and the shape of the base material may be flat, curved, or a combination of these. good. Examples of organic materials include acrylic resins, acrylonitrile resins, polycarbonate resins, polyester resins (e.g., polyethylene terephthalate), styrene resins, cellulose resins, polyolefin resins, vinyl resins (e.g., polyethylene, polyvinyl chloride, vinylbenzyl chloride, etc.). resin, polyvinyl alcohol, etc.), polyvinylidene chloride resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherimide resin, polyethersulfone resin, polysulfone resin, polyvinyl alcohol resin, polyvinyl acetal resin, copolymers thereof, etc. Thermoplastic resins; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins and urethane resins. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, aluminum, titanium, zirconium, niobium, tantalum, and lanthanum, metal oxides thereof, alloys containing these metals, ceramics, and glass. Among these, organic materials are particularly preferable, and at least one of acrylic resins, polyester resins, vinylbenzyl chloride resins, epoxy resins, silicone resins, and urethane resins is more preferable, acrylic resins and polyester resins are more preferable, and polyethylene terephthalate. is particularly preferred.

It is also preferable to disperse inorganic particles, organic particles, rubber particles in the substrate (s), and also colorants such as pigments and dyes, fluorescent brighteners, dispersants, plasticizers, heat stabilizers, light stabilizers. Ingredients such as agents, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants and solvents may also be incorporated.

The thickness of the substrate (s) is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, and may be 500 μm or less, preferably 200 μm or less, more preferably 150 μm. Below, more preferably 100 μm or less, particularly preferably 60 μm or less.

2. Layer (X)
In the laminate of the present invention, a layer (X) different from the substrate (s), the intermediate layer (c), and the water-repellent layer (r) is provided between the substrate (s) and the intermediate layer (c). is preferably provided. Examples of the layer (X) include layers formed from at least one selected from the group (X1) consisting of active energy ray-curable resins and thermosetting resins. The active energy ray is defined as an energy ray that can generate active species by decomposing a compound that generates active species, and includes visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays and An electron beam etc. can be mentioned. The active energy ray-curable resins include acrylic resins, epoxy resins, oxetane resins, urethane resins, polyamide resins, vinylbenzyl chloride resins, vinyl resins (polyethylene, vinyl chloride resins, etc.), styrene. UV-curable resins such as phenol-based resins, phenolic resins, vinyl ether-based resins, silicone-based resins, or mixed resins thereof, and electron beam-curable resins are included, and UV-curable resins are particularly preferred. As group (X1), acrylic resins, silicone resins, styrene resins, vinyl chloride resins, polyamide resins, phenol resins, and epoxy resins are particularly preferable. Further, the layer (X) is at least one selected from the group (X2) consisting of titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide, lanthanum oxide, and SiO ₂ Layers that are formed can also be mentioned. The thickness of the layer (X) is, for example, 0.1 nm or more and 100 μm or less, preferably 1 nm or more and 60 μm or less, more preferably 1 nm or more and 10 μm or less.

2-1. Hard coat layer (hc)
When the layer (X) has a layer formed from at least one selected from the group (X1), the layer (X) can function as a hard coat layer (hc) having surface hardness, The material (s) can be made scratch resistant. The hard coat layer (hc) generally has a pencil hardness of B or higher, preferably HB or higher, more preferably H or higher, and even more preferably 2H or higher. When the layer (X) contains the hard coat layer (hc), that is, when the layer (X) has the function of a hard coat layer, the hard coat layer (hc) may have a single layer structure or a multilayer structure. may The hard coat layer (hc) preferably contains, for example, the above-described UV-curable resin, and particularly preferably contains an acrylic resin or a silicone resin. is preferred. It is also preferable to contain an epoxy-based resin, since there is a tendency for good adhesion with the water-repellent layer (r) via the intermediate layer (c). A specific method for forming the active energy ray-curable resin and the thermosetting resin constituting the group (X1) will be described later in the column of the display device.

When the layer (X) contains the hard coat layer (hc), the hard coat layer (hc) may contain additives. Additives are not limited and include inorganic microparticles, organic microparticles, or mixtures thereof. Examples of additives include ultraviolet absorbers, silica, metal oxides such as alumina, and inorganic fillers such as polyorganosiloxane. By including the inorganic filler, the adhesion to the water-repellent layer (r) via the intermediate layer (c) can be improved. The thickness of the hard coat layer (hc) is, for example, 1 μm or more and 100 μm or less, preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 20 μm or less. When the thickness of the hard coat layer (hc) is 1 μm or more, sufficient scratch resistance can be ensured, and when it is 100 μm or less, flex resistance can be ensured, and as a result, curling due to curing shrinkage can be suppressed. becomes.

2-2. Antireflection layer (ar)
When the layer (X) has a layer formed of at least one selected from the group (X2), the layer (X) functions as an antireflection layer (ar) that prevents reflection of incident light. can be done. When the layer (X) contains an antireflection layer (ar), the antireflection layer (ar) is a layer exhibiting reflection characteristics in which the reflectance is reduced to about 5.0% or less in the visible light region of 380 to 780 nm. is preferably The antireflection layer (ar) preferably comprises a layer formed from silica.

The structure of the antireflection layer (ar) is not particularly limited, and may be a single layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which low refractive index layers and high refractive index layers are alternately laminated is preferable, and the number of laminated layers is preferably 2 to 20 in total. Materials for forming the high refractive index layer include oxides of titanium, zirconium, aluminum, niobium, tantalum, or lanthanum, and materials for forming the low refractive index layer include silica. The multilayered antireflection layer has a structure in which SiO ₂ (silica) and ZrO ₂ or SiO ₂ and Nb ₂ O ₅ are alternately laminated, and the outermost layer on the side opposite to the substrate (s) is SiO ₂ . is preferred. The antireflection layer (ar) can be formed by vapor deposition, for example. The thickness of the antireflection layer (ar) is, for example, 0.1 nm or more and 1000 nm or less.

The layer (X) preferably contains at least the hard coat layer (hc), and may contain both the hard coat layer (hc) and the antireflection layer (ar). When the layer (X) contains both the hard coat layer (hc) and the antireflection layer (ar), the laminate of the present invention comprises, from the substrate side, the substrate (s), the hard coat layer (hc) , the antireflection layer (ar), the intermediate layer (c), and the water-repellent layer (r) are preferably laminated in this order.

3. Intermediate layer (c)
The intermediate layer (c) is a layer formed from the intermediate layer-forming composition, and is preferably a cured layer of the intermediate layer-forming composition. The intermediate layer (c) has a structure derived from the organosilicon compound (C). As described above, in a preferred embodiment, a hydrolyzable group or a hydroxy group is bonded to the silicon atom of the organosilicon compound (C). Therefore, the —SiOH group of the organosilicon compound (C) or the —SiOH group of the organosilicon compound (C) generated by hydrolysis of the hydrolyzable group bonded to the silicon atom is the — derived from the organosilicon compound (C) The intermediate layer (c) should have a condensed structure derived from the organosilicon compound (C) because it undergoes dehydration condensation with SiOH groups or active hydrogen (such as hydroxyl groups) on the surface of the laminate where the intermediate layer (c) is formed. is preferred. The intermediate layer (c) can function as a primer layer for the water-repellent layer (r). The thickness of the intermediate layer (c) is, for example, 1 nm or more and 1000 nm or less.

4. Water-repellent layer (r)
The water-repellent layer (r) is preferably a layer formed from a mixed composition of an organosilicon compound (A) described later (hereinafter sometimes referred to as a composition for forming a water-repellent layer). More preferably, it is a cured layer of a layer-forming composition.

4-1. Organosilicon compound (A)
The organosilicon compound (A) contains a fluoropolyether structure. The fluoropolyether structure can also be referred to as a fluorooxyalkylene group, and means a structure in which both ends are oxygen atoms. Fluoropolyether structures have liquid repellency, such as water repellency or oil repellency. The fluoropolyether structure is preferably a perfluoropolyether structure. The number of carbon atoms contained in the longest linear portion of the fluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and is, for example, 200, preferably 150. The number of silicon atoms in one molecule of the organosilicon compound (A) is preferably 1-10, more preferably 1-6.

The organosilicon compound (A) preferably contains a hydrolyzable group or a hydroxy group (hereinafter both are collectively referred to as a reactive group (h3)) in addition to a fluoropolyether structure and a silicon atom, and the More preferably, the reactive group (h3) is bonded to the silicon atom via a linking group or not via a linking group. The reactive group (h3) forms a water-repellent layer with the organosilicon compound (A), with another monomer, with the organosilicon compound (A), or with the organosilicon compound (A) through a hydrolysis/dehydration condensation reaction. It has the function of bonding through a condensation reaction with active hydrogens (such as hydroxyl groups) on the surface to which the composition is applied. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group and an isocyanate group. The reactive group (h3) is preferably an alkoxy group or a halogen atom, more preferably an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and particularly preferably a methoxy group or an ethoxy group.

In the embodiment in which the organosilicon compound (A) contains a fluoropolyether structure, a silicon atom and a reactive group (h3), a monovalent group having an oxygen atom of the fluoropolyether structure at the terminal on the bond side (hereinafter referred to as an FPE group ), the silicon atom is bonded with or without a linking group, and the silicon atom and the reactive group (h3) are bonded with or without a linking group Bonding is preferred. When the FPE group and the silicon atom are bonded via a linking group, the silicon atom bonded to the reactive group (h3) via the linking group or not via the linking group is the organosilicon compound (A) may be present in one molecule, and the number thereof is, for example, 1 or more and 10 or less.

The FPE group may be linear or may have a side chain, and preferably has a side chain. As an aspect having a side chain, it is particularly preferable that the fluoropolyether structure in the FPE group has a side chain. It preferably has a fluoroalkyl group as a side chain, and the fluoroalkyl group is more preferably a perfluoroalkyl group, still more preferably a trifluoromethyl group. The carbon number of the linking group linking the FPE group and the silicon atom is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less. The FPE group described above is preferably a group in which a fluorine-containing group having a fluoroalkyl group at its end and a perfluoropolyether structure are directly bonded. The fluorine-containing group may be a fluoroalkyl group or a group in which a linking group such as a divalent aromatic hydrocarbon group is bonded to a fluoroalkyl group, but is preferably a fluoroalkyl group. The fluoroalkyl group is preferably a perfluoroalkyl group, more preferably a perfluoroalkyl group having 1 to 20 carbon atoms.

Examples of the fluorine-containing group include CF ₃ (CF ₂ ) _p — (p is, for example, 1 to 19, preferably 1 to 10), CF ₃ (CF ₂ ) _m —(CH ₂ ) _n -, CF ₃ (CF ₂ ) _m -C ₆ H ₄ - (m is 1 to 10, preferably 3 to 7; n is 1 to 5, preferably 2 to 4; CF ₃ (CF ₂ ) _p — or CF ₃ (CF ₂ ) _m —(CH ₂ ) _n — is preferred.

The reactive group (h3) may be bonded to the silicon atom via a linking group, or may be directly bonded to the silicon atom without the linking group, and is directly bonded to the silicon atom. is preferred. The number of reactive groups (h3) bonded to one silicon atom may be 1 or more, and may be 2 or 3, preferably 2 or 3, particularly 3 preferable. When two or more reactive groups (h3) are attached to the silicon atom, different reactive groups (h3) may be attached to the silicon atom, but the same reactive group (h3) may be attached to the silicon atom. preferably combined. When the number of reactive groups (h3) bonded to one silicon atom is 2 or less, the remaining bonds may be bonded with a monovalent group other than the reactive group (h3), for example, An alkyl group (especially an alkyl group having 1 to 4 carbon atoms), H, NCO, etc. can be bonded.

The organosilicon compound (A) is preferably a compound represented by the following formula (a1).

In the above formula (a1),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently a fluorinated alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom ^; When a plurality of Rf ^{a26 are present, a plurality of Rf a26} may be different, when a plurality of Rf ^a27 are present, a plurality of Rf ^a27 may be different, and when a plurality of Rf ^a28 are present, a plurality of Rf ^a28 may be different from each other, and when a plurality of Rf ^a29 are present, the plurality of Rf ^a29 may be different,
R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms; group, at least one of R ²⁵ and R ²⁶ bonded to one carbon atom is a hydrogen atom, and when a plurality of R ²⁵ are present, the ^plurality of R ²⁵ may be different, When doing, multiple R ²⁶ may be different,
R ²⁷ and R ²⁸ are each independently a hydrogen atom, an alkyl group having ¹ to 4 carbon atoms, or a single bond ^; When a plurality of R ²⁸ are present, the plurality of R ²⁸ may be different,
R ²⁹ and R ³⁰ are each independently an alkyl group having ¹ to ²⁰ carbon atoms ^; may have different R ³⁰ ,
M7 is -O-, -C(=O)-O-, -OC(=O)-, -NR-, ^-NRC (=O)-, -C(=O)NR-, - CH═CH— or —C ₆ H ₄ — (phenylene group), R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and M ⁷ is When a plurality of M 7 are present, the plurality of M ⁷ may be different,
M ⁵ is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and when multiple M ⁵ are present, the multiple M ⁵ may be different,
M ¹⁰ is a hydrogen atom or a halogen atom,
M ⁸ and M ⁹ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group; or an ethyl group, and when a plurality of M ⁸ are present, the plurality of M ⁸ may be different, and when a plurality of M ⁹ is present, the plurality of M ⁹ may be different,
f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more,
f26 is an integer from 0 to 20,
f27 is each independently an integer of 0 to 2,
g21 is an integer of 1 to 3, g22 is an integer of 0 to 2, g21 + g22 ≤ 3,
g31 is an integer of 1 to 3, g32 is an integer of 0 to 2, g31 + g32 ≤ 3,
M ¹⁰ -, -Si(M ⁹ ) _g31 (H) _g32 (R ³⁰ ) _{3 -g31-g32} , f21 -{C(R ²⁵ )(R ²⁶ )}-units (U _a1 ), f22 - {C(Rf ^a26 ) (Rf ^a27 )} - unit (U _a2 ), f23 - {Si (R ²⁷ ) (R ²⁸ )} - unit (U _a3 ), f24 - {Si (Rf ^a28 )(Rf ^a29 )}-units (U _a4 ), f 25 -M ⁷ -units (U _a5 ), and f 26 -[C(M ⁵ ){(CH ₂ ) _f27 -Si(M ⁸ ) _g21 (H) _g22 (R ²⁹ ) _3-g21-g22 }]-unit (U _a6 ) has M ¹⁰ - at one end in formula (a1), and -Si(M ⁹ ) _{g31 (H) g32} ₍ R ³⁰ ) _3-g31-g32 is the other terminal, and each unit can be arranged in any order as long as at least a portion thereof forms a fluoropolyether structure and -O- is not continuous with -O- Join side by side. “Arranged in any order and bonded” means that the repeating units are not limited to the order in which the repeating units are consecutively arranged in the order described in formula (a1) above, and f21 units (U _a1 ) are consecutively arranged It means that f21 units in total need not be bonded through other units and may be bonded via other units in the middle. The same applies to the units (U _a2 ) to (U _a6 ) enclosed by f22 to f26.

Further, when at least one of R ²⁷ and R ²⁸ is a single bond, the single bond portion of the unit enclosed by f23 and —O— in M ⁷ are repeatedly bonded to form a branched or cyclic A siloxane bond can be formed.

Rf ^a26 , Rf ^a27 , Rf ^a28 and Rf ^a29 are preferably each independently a fluorine atom or a fluorinated alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. More preferably, it is a fluorine atom or a fluorinated alkyl group having 1 to 2 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms.
R ²⁵ and R ²⁶ are preferably each independently a hydrogen atom or a fluorine atom, at least one of R ²⁵ and R ²⁶ bonded to one carbon atom is a hydrogen atom, more preferably both are hydrogen is an atom.
R ²⁷ and R ²⁸ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.
R ²⁹ and R ³⁰ are preferably C 1-5 alkyl groups, more preferably C 1-2 alkyl groups.
M ⁷ is preferably -C(=O)-O-, -O-, -OC(=O)-, more preferably all -O-.
M ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.
M ¹⁰ is preferably a fluorine atom.
^M8 and ^M9 are preferably each independently an alkoxy group or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom, particularly preferably a methoxy group or an ethoxy group.
Preferably, f21, f23, and f24 are each 1/2 or less of f22, more preferably 1/4 or less, still more preferably f23 or f24 is 0, and particularly preferably f23 and f24 are 0 is.
f25 is preferably 1/5 or more of the total value of f21, f22, f23, and f24 and less than or equal to the total value of f21, f22, f23, and f24.
f21 is preferably 0-20, more preferably 0-15, even more preferably 1-15, and particularly preferably 2-10. f22 is preferably 5 to 600, more preferably 8 to 600, still more preferably 20 to 200, still more preferably 30 to 200, still more preferably 35 to 180, most preferably 40 to 180 is. f23 and f24 are preferably 0 to 5, more preferably 0 to 3, still more preferably 0. f25 is preferably 4-600, more preferably 4-200, even more preferably 10-200, still more preferably 30-60. The total value of f21, f22, f23, f24 and f25 is preferably 20-600, more preferably 20-250, even more preferably 50-230. f26 is preferably 0-18, more preferably 0-15, even more preferably 0-10, still more preferably 0-5. f27 is preferably 0 to 1, more preferably 0. g21 and g31 are each independently preferably 2 to 3, more preferably 3. g22 and g32 are each independently preferably 0 or 1, more preferably 0. g21+g22 and g31+g32 are preferably three.

In the above formula (a1), both R ²⁵ and R ²⁶ are hydrogen atoms, and Rf ^a26 and Rf ^a27 are fluorine atoms or C 1-2 fluorinated alkyl groups in which all hydrogen atoms are substituted with fluorine atoms. wherein M ⁷ is all —O—, M ⁸ and M ⁹ are all methoxy, ethoxy or chlorine atoms (especially methoxy or ethoxy), M ⁵ is hydrogen and M ¹⁰ is a fluorine atom, f21 is 1 to 10 (preferably 2 to 7), f22 is 30 to 200 (more preferably 40 to 180), f23 and f24 are 0, f25 is 30 to 60, and f26 is 0 to 6 , f27 is 0 to 1 (especially preferably 0), g21 and g31 are 1 to 3 (both are preferably 2 or more, more preferably 3), g22 and g32 are 0 to 2 (any is preferably 0 or 1, more preferably 0), and the compound (a11) in which g21+g22 and g31+g32 are 3 is preferably used as the organosilicon compound (A).

The organosilicon compound (A) is preferably represented by the following formula (a2).

In the above formula (a2),
Rf ^a1 is a divalent fluoropolyether structure having oxygen atoms at both ends,
R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having 1 to ²⁰ carbon atoms, and when there are a plurality of R ¹¹ , the plurality of R ¹¹ may be different from each other; When present, multiple R ¹² may be different, and when multiple R ¹³ are present, multiple R ¹³ may be different,
E ¹ , E ² , E ³ , E ⁴ and E ⁵ ^each independently represent ^a hydrogen atom or a fluorine atom; When a plurality of ² are present, a plurality of E ² may be different, when a plurality of E ³ are present, a plurality of E ³ may be different, and when a plurality of E ⁴ is present, a plurality of E ⁴ may be different, and when multiple E ⁵ are present, the multiple E ⁵ may be different,
G ¹ and G ² are each independently a divalent to decavalent organosiloxane group having a siloxane bond,
J ¹ , J ² , and J ³ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group or an ethyl group, and when there are a plurality of J ¹ , the plurality of J ¹ may be different, and when there are a plurality of J ² , the plurality of J ² may be different, and J When there are multiple ³ 's, the multiple J ³ 's may be different,
L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom, a silicon atom or a fluorine atom, and -{C(R ²⁵ )(R ²⁶ )}-unit (U _a1 ),-{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ),-{Si(R ²⁷ )(R ²⁸ )}-unit (U _a3 ) Or, at least one -M ⁷ - unit (U _a5 ) is a linking group that is arranged in any order (R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , Rf ^a26 , Rf ^a27 and M ⁷ are the above the same as in formula (a1)),
a10 and a14 are each independently 0 or 1,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0 to 9;
a13 is 0 to 4;
When a11 is 0, or when a11 is 1 and G ¹ has a valence of 2, d11 is 1, and when a11 is 1 and G ¹ has a valence of 3 to 10, d11 is the value of G ¹ is one less than the number,
When a15 is 0, or when a15 is 1 and G ² is divalent, d12 is 1, and when a15 is 1 and G ² is 3 to 10 valent, d12 is the value of G ² is one less than the number,
a21 and a23 are each independently 0 to 2,
e11 is 1 to 3, e12 is 0 to 2, e11 + e12 ≤ 3,
e21 is 1 to 3, e22 is 0 to 2, e21 + e22 ≤ 3,
e31 is 1 to 3, e32 is 0 to 2, and e31+e32≦3.

Note that a10 is 0 means that the portion enclosed with a10 is a single bond, and even if a11, a12, a13, a14, a15, a16, a21 or a23 is 0 It is the same.

Rf ^a1 is preferably -O-(CF ₂ CF ₂ O) _e4 -, -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, -O-(CF ₂ -CF(CF ₃ )O) _e6 - . Both e4 and e5 are 15-80, and e6 is 3-60. Rf ^a1 is also preferably a group in which hydrogen atoms are removed from hydroxyl groups at both ends of a structure obtained by randomly dehydrating and condensing p mol of perfluoropropylene glycol and q mol of perfluoromethanediol, and p+q is It is from 15 to 80, and this aspect of Rf ^a1 is most preferable.

R ¹¹ , R ¹² and R ¹³ are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

Each of E ¹ , E ² , E ³ and E ⁴ is preferably a hydrogen atom, and E ⁵ is preferably a fluorine atom.

L ¹ and L ² each independently represent -{C(R ²⁵ )(R ²⁶ )}-unit (U _a1 ) or -{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ) A divalent linking group having 1 to 12 carbon atoms (preferably 1 to 10, more preferably 1 to 5) containing a fluorine atom in which one or more of are bonded in any order is preferable, and x is 1 to 12 (preferably 1 to 10, more preferably 1 to 5) is more preferably -(CF ₂ ) _x -.

G ¹ and G ² are each independently preferably a divalent to pentavalent organosiloxane group having a siloxane bond.

J ¹ , J ² and J ³ are each independently preferably methoxy, ethoxy or --(CH ₂ ) _e7 --Si(OR ¹⁴ ) ₃ , more preferably methoxy or ethoxy.

a10 is preferably 1, a11 is preferably 0, a12 is preferably 0 to 7, more preferably 0 to 5, a13 is preferably 1 to 3, a14 is preferably 1, a15 is preferably 0, a16 is preferably 0 to 6, more preferably 0 to 3, both a21 and a23 are preferably 0 or 1 (more preferably both are 0), d11 is preferably 1, d12 is preferably 1, e11, Both e21 and e31 are preferably 2 or more, and 3 is also preferable. Each of e12, e22 and e32 is preferably 0 or 1, more preferably 0. Preferably, e11+e12, e21+e22, and e31+e32 are all three. These preferred ranges may be satisfied singly or in combination of two or more.

As the organosilicon compound (A), Rf ^a1 in the above formula (a2) is a structure in which p mol of perfluoropropylene glycol and q mol of perfluoromethanediol are randomly dehydrated and condensed. A group left after being removed (p + q = 15 to 80), both L ¹ and L ² are perfluoroalkylene groups having 1 to 5 carbon atoms (preferably 1 to 3), and E ¹ , E ² , and E3 is a hydrogen atom ^, ^E4 is a hydrogen atom, ^E5 is ^a fluorine atom, and J1, J2, and ^J3 ^are all a methoxy group or an ethoxy group (especially a methoxy group); , a10 is 1, a11 is 0, a12 is 0 to 7 (preferably 0 to 5), a13 is 2, a14 is 1, a15 is 0, a16 is 0 to 6 (especially 0), a21 and a23 are each independently 0 or 1 (more preferably both a21 and a23 are 0), d11 is 1, d12 is 1, e11, Compound (a21) wherein e21 and e31 are all 2 to 3 (especially 3), e12, e22 and e32 are all 0 or 1 (especially 0), and e11+e12, e21+e22, and e31+e32 are all 3 is preferably used.

As the organosilicon compound (A), Rf ^a1 in the above formula (a2) is —O—(CF ₂ CF ₂ CF ₂ O) _e5 —, e5 is 15 to 80 (preferably 25 to 40), L ¹ is a divalent linking group having 3 to 6 carbon atoms containing a fluorine atom and an oxygen atom, L ² is a perfluoroalkylene group having 2 to 10 carbon atoms, and both E ² and E ³ are hydrogen atoms. E ⁵ is a fluorine atom, J ² is —(CH ₂ ) _e7 —Si(OCH ₃ ) ₃ , e7 is 2 to 4, a10 is 1, a11 is 0, a12 is 0, a13 is 2, a14 is 1, a15 is 0, a16 is 0, d11 is 1, d12 is 1, and e21 is 3 (a22 ) is also preferred.

More specifically, the organosilicon compound (A) includes compounds of the following formula (a3).

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ³¹ is a structure in which p mol of perfluoropropylene glycol and q mol of perfluoromethanediol are randomly dehydrated and condensed. A group (p + q is 15 to 80) remaining after hydrogen atoms are removed from both terminal hydroxyl groups or a group remaining after hydrogen atoms are removed from both terminal hydroxyl groups of perfluorooxyalkylene glycol having 15 to 240 carbon atoms ( The former group is more preferable as R ³¹ ), R ³² is a perfluoroalkylene group having 1 to 10 carbon atoms, R ³³ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R ³⁴ is an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms in R ³⁰ is preferably 1-4, more preferably 1-3. The number of carbon atoms in R ³² is preferably 1-5. h1 is 1 to 10, preferably 1 to 8, more preferably 1 to 6. h2 is 1 or more, preferably 2 or more, and may be 3.

As the organosilicon compound (A), a compound represented by the following formula (a4) can also be mentioned.

In the above formula (a4), R ⁴⁰ is a C 2-5 perfluoroalkyl group, R ⁴¹ is a C 2-5 perfluoroalkylene group, and R ⁴² is a C 2-5 a fluoroalkylene group in which some of the hydrogen atoms of the alkylene group are substituted with fluorine, R ⁴³ and R ⁴⁴ are each independently an alkylene group having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group; be. k1 is an integer of 1-5. k2 is an integer of 1 to 3, preferably 2 or more, and may be 3.

The number average molecular weight of the organosilicon compound (A) is preferably 2,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 6,000 or more, and particularly preferably 7,000 or more. 000 or more, preferably 40,000 or less, more preferably 20,000 or less, and still more preferably 15,000 or less.

As the organosilicon compound (A), only one type may be used, or two or more types may be used.

The composition for forming a water-repellent layer is a mixed composition of the organosilicon compound (A), and is obtained by mixing the organosilicon compound (A). When components other than the organosilicon compound (A) are mixed, the water-repellent layer-forming composition can be obtained by mixing the organosilicon compound (A) with the other components. The composition for forming a water-repellent layer includes those that have undergone reaction after being mixed, for example, during storage. As an example in which the reaction has progressed, for example, the composition for forming a water-repellent layer has a hydrolyzable group bonded (which may be bonded via a linking group) to the silicon atom of the organosilicon compound (A). includes a compound that has become a —SiOH group (Si and OH may be bonded via a linking group) by hydrolysis. Further, the composition for forming a water-repellent layer may contain a condensate of the organosilicon compound (A). The -SiOH group (Si and OH may be bonded via a linking group) of the resulting organosilicon compound (A) is a -SiOH group derived from the organosilicon compound (A) (Si and OH are linking groups. may be bonded via), or condensates formed by dehydration condensation with —SiOH groups derived from other compounds.

When the water-repellent layer (r) is a layer formed from the water-repellent layer-forming composition, the water-repellent layer (r) has a structure derived from the organosilicon compound (A). As described above, in a preferred embodiment, the organosilicon compound (A) has a hydrolyzable group or a hydroxy group bonded to a silicon atom (which may be bonded via a linking group), and the organosilicon compound The —SiOH group of (A) or the —SiOH group of the organosilicon compound (A) generated by hydrolysis (Si and OH may be bonded via a linking group) is derived from the organosilicon compound (A). -SiOH group (Si and OH may be bonded via a linking group), -SiOH group derived from another compound, or active hydrogen on the surface where the water-repellent layer (r) is formed in the laminate ( hydroxyl group, etc.), the water-repellent layer (r) preferably has a condensed structure derived from the organosilicon compound (A).

4-2. Organosilicon compound (B)
The composition for forming a water-repellent layer may further contain an organosilicon compound (B) represented by the following formula (b1). When the organic silicon compound (B) is mixed with the water-repellent layer-forming composition, the water-repellent layer-forming composition is obtained by mixing the organic silicon compound (A) and the organic silicon compound (B). . The organosilicon compound (B) is present between the organosilicon compounds (A) in the cured film, and has the effect of further improving the slideability of water droplets and the like. The organosilicon compound (B) has a hydrolyzable group or a hydroxy group represented by ^A2 , as will be described later. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group and an isocyanate group.

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom;
R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^b11 are present, the plurality of R ^b11 are different from each other. When there are a plurality of R ^b12 , the plurality of R ^b12 may be different, when there are a plurality of R ^b13 , the plurality of R ^b13 may be different, and when there is a plurality of R ^b14 may be different from each other in a plurality of R ^b14 ,
Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^b11 are present When there is a plurality of Rf b11, the plurality of Rf ^b11 may be different, when there are a plurality of Rf ^b12 , the plurality of Rf ^b12 may be different, and when there is a plurality of Rf ^b13 , the plurality of Rf ^b13 may be different. may be present, and if there are a plurality of Rf ^b14 , the plurality of Rf ^b14 may be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^b15 are present, the plurality of R ^b15 may be different,
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- and R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and when there are multiple A ¹ , the multiple A ¹ may be different,
A ² is a hydrolyzable group or a hydroxy group, and when a plurality of A ² are present, the plurality of A ² may be different,
b11, b12, b13, b14, and b15 are each independently an integer of 0 to 100,
c is an integer from 1 to 3,
Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-unit (U _b1 ), b12 -{C(Rf ^b11 ) (Rf ^b12 )}-unit (U _b2 ), b13-{Si(R ^b13 )(R ^b14 )}-unit (U _b3 ), b14-{Si(Rf ^b13 )(Rf ^b14 )} - unit (U _b4 ), b15 -A ¹ - units (U _b5 ), Rf ^b10 - becomes one terminal of the compound represented by formula (b1), -Si(A ² ) _c (R ^b15 ) Each unit (U _b1 ) to unit (U _b5 ) is optional as long as _3-c is the other end, does not form a fluoropolyether structure, and -O- is not linked to -O- to -F Arrange and join in order.

Each Rf ^b10 is independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms).

R ^b11 , R ^b12 , R ^b13 and R ^b14 are preferably hydrogen atoms.

R ^b15 is preferably an alkyl group having 1 to 5 carbon atoms.

A ¹ is preferably -O-, -C(=O)-O-, or -OC(=O)-.

A ² is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom.

b11 is preferably 1-30, more preferably 1-25, still more preferably 1-10, particularly preferably 1-5, most preferably 1-2.

b12 is preferably 0-15, more preferably 0-10.

b13 is preferably 0-5, more preferably 0-2.

b14 is preferably 0-4, more preferably 0-2.

b15 is preferably 0-4, more preferably 0-2.

c is preferably 2 to 3, more preferably 3.

The total value of b11, b12, b13, b14, and b15 is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 80 or less, more preferably 50 or less, and still more preferably 20. It is below.

In particular, Rf ^b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, both R ^b11 and R ^b12 are hydrogen atoms, A ² is a methoxy group or an ethoxy group, and b11 is 1 to 5, b12 is 0 to 5, b13, b14, and b15 are all 0, and c is 3.

In the examples described later, when FAS13E used as the organosilicon compound (B) is represented by the above formula (b1), R ^b11 and R ^b12 are both hydrogen atoms, b11 is 2, b13, b14, and b15 are All are 0, c is 3, A ² is an ethoxy group, Rf ^b10 -{C(Rf ^b11 )(Rf ^b12 )} _b12 - is the terminal and is defined to be C ₆ F ₁₃ -.

Specific examples of the compounds represented by the above formula (b1) include C _j F _2j+1 -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is an integer of 1 to 12), among which C ₄ F ₉ —Si—(OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ —Si—(OC ₂ H ₅ ) ₃ , C ₇ F ₁₅ — Si--(OC ₂ H ₅ ) ₃ and C ₈ F ₁₇ --Si--(OC ₂ H ₅ ) ₃ are preferred. Also, _CF3CH2O ( _CH2 ) _kSiCl3 , _CF3CH2O ₍ _CH2 ) _kSi ₍ _OCH3 ) ₃ _, _CF3CH2O ₍ _CH2 ) _kSi ₍ _OC2H5 ) ₃ , _CF3 ( _CH2 )2Si( _CH3 ) ₂ ( _CH2 ) _kSiCl3 , _CF3 ( _CH2 ) _2Si(CH3)2 ₍ _CH2 ₎ _kSi ₍ OCH3) ₃ _, _CF3 ₍ _CH2 )2Si( _CH3 ) ₂ ( _CH2 ) _kSi ( _OC2H5 ) ₃ , _CF3 ( _CH2 ) _6Si ( _CH3 ) ₂ ₍ _CH2 ) _kSiCl3 _, _CF3 ₍ _CH2 ) _6Si ( _CH3 ) ₂ ( _CH2 ) _kSi (OCH3) ₃ , _CF3 ₍ _CH2 ) _6Si ( _CH3 ) ₂ ( _CH2 ) _kSi ( _OC2H5 ) ₃ _, _CF3COO (CH ₂ ) _k SiCl ₃ , CF ₃ COO(CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ COO(CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ (k is 5 to 20). and preferably 8 to 15). Also, _CF3 (CF2) _m- ( _CH2 ) _nSiCl3 , _CF3 ( _CF2 ) _m- ( _CH2 ₎ _nSi (OCH3) ₃ , _CF3 ₍ _CF2 ) _m- ₍ _CH2 ) _n Si(OC ₂ H ₅ ) ₃ (where m is 0 to 10, preferably 0 to 7, n is 1 to 5, preferably 2 to 4). ). CF ₃ (CF ₂ ) _p —(CH ₂ ) _q —Si—(CH ₂ CH═CH ₂ ) ₃ may also be mentioned, where p is 2 to 10, preferably 2 to 8, q are all 1 to 5, preferably 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p —(CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p —(CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p —( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (where p is 2 to 10, preferably 3 to 7, q is 1 to 5, preferably 2 to 4 is).

Among the compounds represented by the above formula (b1), the compounds represented by the following formula (b2) are preferable.

In the above formula (b2), R ⁶⁰ is a perfluoroalkyl group having 1 to 8 carbon atoms, R ⁶¹ is an alkylene group having 1 to 5 carbon atoms, and R ⁶² is an alkyl group having 1 to 3 carbon atoms. .

As described above, the composition for forming a water-repellent layer includes a composition that has undergone a reaction after mixing the organosilicon compound (A) and the optionally used organosilicon compound (B), and the reaction has proceeded. For example, the composition for forming a water-repellent layer may contain a compound in which the hydrolyzable group bonded to the silicon atom of the organosilicon compound (B) is hydrolyzed to form a —SiOH group. Further, the mixed composition may contain a condensate of the organosilicon compound (B), and the condensate may be a —SiOH group possessed by the organosilicon compound (B) or an organosilicon compound produced by hydrolysis ( Condensates formed by dehydration condensation of —SiOH groups of B) with —SiOH groups derived from the organosilicon compound (B) or —SiOH groups derived from other compounds are exemplified.

When the organosilicon compound (B) is mixed with the water-repellent layer-forming composition, the water-repellent layer (r) has a structure derived from the organosilicon compound (B). The organosilicon compound (B) represented by the above formula (b1) has a hydrolyzable group or a hydroxy group represented by A ² , and the —SiOH group or hydrolyzed The —SiOH groups of the organosilicon compound (B) generated in the above are —SiOH groups derived from the organosilicon compound (B), —SiOH groups derived from other compounds, or the water-repellent layer (r) is formed in the laminate. The water-repellent layer (r) preferably has a condensed structure derived from the organosilicon compound (B) because it undergoes dehydration condensation with the active hydrogen (such as hydroxyl group) on the surface.

4-3. Solvent 4
The water-repellent layer-forming composition is usually mixed with a solvent 4 . As the solvent 4, it is preferable to use a fluorine-based solvent. For example, a fluorinated ether-based solvent, a fluorinated amine-based solvent, a fluorinated hydrocarbon-based solvent, etc. can be used. preferable. As the fluorinated ether-based solvent, hydrofluoroethers such as fluoroalkyl (especially perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl (especially methyl group or ethyl group) ether are preferable. Fluoroisobutyl ether may be mentioned. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec® 7200 (manufactured by 3M, molecular weight about 264). As the fluorinated amine-based solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferable, and a third Preferred are class amines, specifically tris(heptafluoropropyl)amine, and Fluorinert® FC-3283 (manufactured by 3M, molecular weight about 521) corresponds to this. Fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane and perfluorohexane, and 1,3-bis(trifluoromethylbenzene). Examples include fluorinated aromatic hydrocarbon solvents. Examples of 1,1,1,3,3-pentafluorobutane include Solv 55 (manufactured by Solvex).

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC) and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by AGC) can be used. can.

As the solvent 4, it is preferable to use at least a fluorinated amine solvent. As the solvent 4, it is preferable to use two or more kinds of fluorine-based solvents, and it is preferable to use a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (especially a fluorinated aliphatic hydrocarbon-based solvent).

The amount of the organosilicon compound (A) is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, when the entire composition for forming a water-repellent layer is 100% by mass, Moreover, it is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

The amount of the organosilicon compound (B) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, when the entire composition for forming a water-repellent layer is 100% by mass, Moreover, it is preferably 0.3% by mass or less, more preferably 0.2% by mass or less.

The mass ratio of the organosilicon compound (B) to the organosilicon compound (A) is preferably 0.2 or more, more preferably 0.4 or more, and preferably 3.0 or less, more preferably 1.0. 5 or less.

The total content of the organosilicon compound (A), the organosilicon compound (B), and the solvent 4 is, for example, 90% by mass or more, preferably 95% by mass or more, more preferably 95% by mass or more, based on 100% by mass of the water-repellent layer-forming composition. is 99% by mass or more, and may be 100% by mass.

In addition, the water-repellent layer-forming composition contains a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, and an antiviral agent, as long as the effects of the present invention are not impaired. , biofouling inhibitors, deodorants, pigments, flame retardants, antistatic agents and the like may be mixed. The amount of the additive is preferably 5% by mass or less, more preferably 1% by mass or less, based on 100% by mass of the composition for forming a water-repellent layer.

The thickness of the water-repellent layer (r) is, for example, about 1 to 1000 nm.

5. Characteristics of Laminate The water contact angle (initial contact angle) of the surface of the water-repellent layer (r) of the laminate of the present invention is, for example, 105° or more, preferably 110° or more, and for example, 125° or less.

The sliding angle (initial sliding angle) of water on the surface of the water-repellent layer (r) of the laminate of the present invention is, for example, 30° or less, preferably 28° or less, and for example, 10° or more.

The surface of the water-repellent layer (r) of the laminate of the present invention was subjected to an abrasion resistance test in which a load of 1000 g was applied to the area of a circle with a diameter of 6 mm and rubbed back and forth 3000 times. The water contact angle (initial wear resistance) on the surface is, for example, 105° or more, preferably 110° or more, and is, for example, 125° or less. The abrasion resistance test is a test in which the water repellent layer (r) side surface of the laminate of the present invention is rubbed back and forth 3000 times with a load of 1000 g on the area of a circle with a diameter of 6 mm. Rubbing with a body (preferably an eraser) is preferred. For example, it is preferable to use an eraser, set the stroke distance in the abrasion resistance test to 40 mm, set the rubbing speed to 40 reciprocations/minute, and measure the contact angle at approximately the center of the stroke area. When the load is applied, it is sufficient that a pressure equivalent to applying a load of 1000 g per area of a circle with a diameter of 6 mm is applied.

When the laminate of the present invention was produced using the composition for forming an intermediate layer after an accelerated test of stirring in an atmosphere of 22° C. and 55% humidity for 2 hours, on the surface of the water-repellent layer (r) of the laminate, The water contact angle (abrasion resistance after accelerated test) on the surface of the water-repellent layer (r) is , for example 90° or more, preferably 100° or more, more preferably 105° or more, and for example 120° or less. The wear resistance test was the same as the wear resistance test for measuring the initial wear resistance, except that the number of times of rubbing was reciprocated 1500 times.

A specific method for evaluating each characteristic will be described in detail in the Examples section.

6. Method for Manufacturing Laminate Next, a method for manufacturing the laminate of the present invention will be described.

The method for producing the laminate of the present invention includes (i) the step of forming the intermediate layer (c) on the substrate (s), and (ii) the step of forming the water-repellent layer (r).

In the step (i), the intermediate layer-forming composition is applied to the substrate (s) or the layer (X) provided on the substrate (s). Examples of the method for applying the intermediate layer-forming composition include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, gravure coating, and particularly bar coating. , spin coating, die coating, and gravure coating are preferred.

It is preferable to subject the substrate (s) or the layer (X) provided on the substrate (s) to an easy-adhesion treatment before applying the intermediate layer-forming composition. Hydrophilic treatment such as corona treatment, plasma treatment, ultraviolet treatment, etc., can be mentioned as the easy-adhesion treatment. By performing an easy adhesion treatment such as plasma treatment, OH groups (especially when the material of the base material (s) or layer (X) is an epoxy resin) or COOH groups are formed on the surface of the base material (s) or layer (X). (especially when the material of the substrate (s) or layer (X) is an acrylic resin) can be formed, and such functional groups are formed on the surface on which the intermediate layer (c) is to be formed. In particular, the adhesion between the intermediate layer (c) and the substrate (s) or between the intermediate layer (c) and the layer (X) is further improved. In particular, it is preferable to subject the substrate (s) or the layer (X) formed from the group (X1) to an easy-adhesion treatment.

When the layer (X) is formed from at least one selected from the group (X1), for example, the layer (X) is based on a composition containing a reactive material that forms a crosslinked structure upon irradiation with an active energy ray or thermal energy. The layer (X) can be formed by coating on the material (s) and curing. Moreover, when the layer (X) is formed from at least one selected from the group (X2), the layer (X) can be formed, for example, by a vapor deposition method.

After applying the intermediate layer forming composition, the intermediate layer (c) can be formed by curing at room temperature or by heating. Curing conditions are not particularly limited, and may be left at room temperature in the air for, for example, 10 seconds or more. In the present invention, normal temperature means 5 to 60°C, and the intermediate layer (c) can be formed by standing still at a temperature range of preferably 15 to 40°C. After that, it may be further heated (calcined) at a temperature of 50 to 300° C., preferably 100 to 200° C., for about 10 seconds to 60 minutes.

After the intermediate layer forming composition is applied to form the intermediate layer (c), the water repellent layer forming composition is applied and cured at room temperature or by heating to form the water repellent layer (r). can be formed.

The water-repellent layer (r) can be formed by applying the water-repellent layer-forming composition onto the intermediate layer (c) and drying it. Examples of methods for applying the water-repellent layer-forming composition include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating.

The conditions after the water-repellent layer-forming composition is applied onto the intermediate layer (c) are not particularly limited, and the water-repellent layer (r) is formed by allowing the composition to stand at room temperature in the air for 10 seconds or longer, for example. can be formed. After that, it may be further heated (calcined) at a temperature of 50 to 300° C., preferably 100 to 200° C., for about 10 seconds to 60 minutes.

<Display device>
The laminate of the present invention is suitable for use in display devices, and particularly suitable for flexible display devices. The laminate of the present invention can preferably be used as a front plate in a display device, and the front plate is sometimes called a window film.

The display device preferably comprises a display device laminate containing a window film (that is, the laminate of the present invention) and an organic EL display panel. body is placed. Further, in the flexible display device, it is preferable that the laminate for a flexible display device including a window film having flexible characteristics and an organic EL display panel are provided. A laminate is arranged and configured to be foldable. The laminate for a display device (preferably a laminate for a flexible display device) may further contain a polarizing plate (preferably a circularly polarizing plate), a touch sensor, etc. to constitute a touch panel display, and the order of lamination thereof is arbitrary. However, it is preferable that the layers are laminated in the order of the window film, the polarizing plate and the touch sensor, or in the order of the window film, the touch sensor and the polarizing plate from the viewing side. When the polarizing plate is present on the viewing side of the touch sensor, the pattern of the touch sensor becomes less visible and the visibility of the displayed image is improved, which is preferable. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like. Also, the display device (preferably flexible display device) can comprise a light shielding pattern formed on at least one surface of any one of the window film, the polarizing plate and the touch sensor.

(window film)
The window film is arranged on the viewing side of the display device (preferably the flexible image display device) and plays a role of protecting other components from external shocks or environmental changes such as temperature and humidity. Glass may be used as such a protective layer, and in a flexible image display device, a material having flexible properties may be used for the window film instead of being rigid and hard like glass. Therefore, when the laminate of the present invention is used as a window film in a flexible display device, the substrate (s) is preferably made of a flexible transparent substrate, and at least one surface of the substrate (s) is coated with a hard coat. Layers may be laminated.

The transparent substrate has a visible light transmittance of, for example, 70% or more, preferably 80% or more. Any transparent polymer film can be used as the transparent substrate. Specifically, polyolefins such as polyethylene, polypropylene, polymethylpentene, norbornene, or cycloolefin derivatives having a monomer unit containing cycloolefin, (modified) cellulose such as diacetyl cellulose, triacetyl cellulose, and propionyl cellulose acrylics such as methyl methacrylate (co)polymers, polystyrenes such as styrene (co)polymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers Polyvinyl chlorides, polyvinylidene chlorides, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polycarbonate and polyarylate, polyamides such as nylon, polyimides, polyamideimides, polyetherimides, Films formed of polymers such as polyethersulfones, polysulfones, polyvinyl alcohols, polyvinyl acetals, polyurethanes, and epoxy resins may be used, and unstretched, monoaxially or biaxially stretched films are used. be able to. These polymers can be used alone or in combination of two or more. Among the transparent substrates described above, preferred are polyamide films, polyamideimide films, polyimide films, polyester films, olefin films, acrylic films, and cellulose films, which are excellent in transparency and heat resistance. It is also preferable to disperse inorganic particles such as silica, organic fine particles, rubber particles, etc. in the polymer film. In addition, colorants such as pigments and dyes, optical brighteners, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants, solvents, etc. may contain a compounding agent. The thickness of the transparent substrate is 5 μm or more and 200 μm or less, preferably 20 μm or more and 100 μm or less. Particularly when used in a flexible image display device, the thickness of the transparent substrate is preferably 5 μm or more and 60 μm or less.

The hard coat layer when the laminate of the present invention is used as a window film is also the same as the hard coat layer (hc) described above. As described above, the hard coat layer (hc) is preferably formed from an active energy ray-curable resin and a thermosetting resin. It can be formed by curing a hardcoat composition containing the forming reactive material. The hard coat composition contains at least one polymer of a radically polymerizable compound and a cationic polymerizable compound.

The radically polymerizable compound is a compound having a radically polymerizable group. The radically polymerizable group possessed by the radically polymerizable compound may be any functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group and a (meth)acryloyl group. When the radically polymerizable compound has two or more radically polymerizable groups, these radically polymerizable groups may be the same or different. The number of radically polymerizable groups in one molecule of the radically polymerizable compound is preferably two or more from the viewpoint of improving the hardness of the hard coat layer. The radically polymerizable compound is preferably a compound having a (meth)acryloyl group from the viewpoint of high reactivity, and a polyfunctional acrylate monomer having 2 to 6 (meth)acryloyl groups in one molecule. Compounds called epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and oligomers having several (meth) acryloyl groups in the molecule and having a molecular weight of several hundred to several thousand are preferred. Available. It preferably contains one or more selected from epoxy (meth)acrylate, urethane (meth)acrylate and polyester (meth)acrylate.

The cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, or a vinyl ether group. The number of cationically polymerizable groups in one molecule of the cationically polymerizable compound is preferably two or more, more preferably three or more, from the viewpoint of improving the hardness of the hard coat layer. As the cationically polymerizable compound, among others, a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable. A cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint that shrinkage accompanying a polymerization reaction is small. In addition, among the cyclic ether groups, compounds having epoxy groups are readily available in various structures, do not adversely affect the durability of the resulting hard coat layer, and are easy to control compatibility with radically polymerizable compounds. There is an advantage. In addition, among the cyclic ether groups, the oxetanyl group tends to have a higher degree of polymerization than the epoxy group, is less toxic, accelerates the rate of network formation obtained from the cationically polymerizable compound in the resulting hard coat layer, and radicals It has the advantage of forming an independent network without leaving unreacted monomers in the film even in a region where the polymerizable compound is mixed.

Examples of cationic polymerizable compounds having an epoxy group include polyglycidyl ethers of polyhydric alcohols having an alicyclic ring, or compounds containing cyclohexene rings or cyclopentene rings, which are treated with a suitable oxidizing agent such as hydrogen peroxide or peracid. Alicyclic epoxy resin obtained by epoxidation; polyglycidyl ether of aliphatic polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer of glycidyl (meth)acrylate, Aliphatic epoxy resins such as copolymers; bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or derivatives such as alkylene oxide adducts and caprolactone adducts thereof, and glycidyl ethers produced by reaction with epichlorohydrin, and glycidyl ether type epoxy resins derived from bisphenols such as novolak epoxy resins.
The hard coat composition may further include a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., and can be appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cationic polymerization.

Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization by at least one of active energy ray irradiation and heating. Examples of thermal radical polymerization initiators include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile.
As active energy ray radical polymerization initiators, Type 1 type radical polymerization initiators that generate radicals by decomposition of molecules and Type 2 type radical polymerization initiators that generate radicals by hydrogen abstraction type reaction in coexistence with tertiary amines are used. Yes, each can be used alone or in combination.

The cationic polymerization initiator should be capable of releasing a substance that initiates cationic polymerization by at least one of active energy ray irradiation and heating. As cationic polymerization initiators, aromatic iodonium salts, aromatic sulfonium salts, cyclopentadienyl iron (II) complexes and the like can be used. Depending on their structural differences, they can initiate cationic polymerization either by irradiation with active energy rays or by heating.

The polymerization initiator can be included in an amount of 0.1 to 10% by weight with respect to 100% by weight of the hard coat composition as a whole. If the content of the polymerization initiator is less than 0.1% by weight, curing may not proceed sufficiently, and it may be difficult to realize the mechanical properties and adhesion of the finally obtained coating film. If the content is more than % by weight, adhesion failure, cracking, and curling may occur due to cure shrinkage.

The hard coat composition may further contain one or more selected from the group consisting of solvents and additives. The solvent is capable of dissolving or dispersing the polymerizable compound and the polymerization initiator, and any solvent known as a solvent for hard coat compositions in this technical field can be used without limitation. The additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.

(Circularly polarizing plate)
As described above, the display device (preferably flexible display device) of the present invention preferably includes a polarizing plate, especially a circularly polarizing plate. A circularly polarizing plate is a functional layer having a function of transmitting only a right-handed or left-handed circularly polarized light component by laminating a λ/4 retardation plate on a linearly polarizing plate. For example, by converting external light into right-handed circularly polarized light and blocking the left-handed circularly polarized light reflected by the organic EL panel, and allowing only the luminescent component of the organic EL to pass through, the effect of the reflected light is suppressed to create an image. used to make it easier to see. In order to achieve the circular polarization function, the absorption axis of the linear polarizer and the slow axis of the λ/4 retardation plate should theoretically be 45 degrees, but in practice they are 45±10 degrees. The linear polarizing plate and the λ/4 retardation plate do not necessarily have to be laminated adjacent to each other as long as the relationship between the absorption axis and the slow axis satisfies the above range. Although it is preferable to achieve perfect circular polarization at all wavelengths, it is not always necessary in practice, so the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable to further laminate a λ/4 retardation film on the visible side of the linear polarizing plate to circularly polarize the emitted light, thereby improving the visibility when wearing polarized sunglasses.

A linear polarizer is a functional layer that passes light oscillating in the direction of the transmission axis, but blocks the polarization of the oscillating component perpendicular to it. The linear polarizing plate may have a configuration including a linear polarizer alone or a linear polarizer and a protective film attached to at least one surface of the linear polarizer. The thickness of the linear polarizing plate may be 200 μm or less, preferably 0.5 μm or more and 100 μm or less. When the thickness of the linear polarizing plate is within the above range, the flexibility of the linear polarizing plate tends to be less likely to decrease.

The linear polarizer may be a film-type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) film. A dichroic dye such as iodine is adsorbed on a PVA-based film that has been oriented by stretching, or the film is stretched while adsorbed to PVA, thereby aligning the dichroic dye and exhibiting polarizing performance. The production of the film-type polarizer may include other steps such as swelling, cross-linking with boric acid, washing with an aqueous solution, and drying. The stretching and dyeing processes may be carried out on the PVA-based film alone, or may be carried out while it is laminated with another film (stretching resin base material) such as polyethylene terephthalate. The thickness of the PVA-based film used is preferably 3 to 100 μm, and the draw ratio is preferably 2 to 10 times. As a method for producing a laminate of a stretchable resin base material and a PVA-based resin layer, a method of applying a coating liquid containing a PVA-based resin to the surface of the stretchable resin base material and drying it is preferable.

In particular, if the manufacturing method includes the step of stretching and dyeing the PVA-based resin layer and the resin substrate for stretching in the state of a laminate, even if the PVA-based resin layer is thin, it is supported by the resin substrate for stretching. Thus, the film can be stretched without problems such as breakage due to stretching.

The thickness of the polarizer is 20 μm or less, preferably 12 μm or less, more preferably 9 μm or less, even more preferably 1 to 8 μm, particularly preferably 3 to 6 μm. If it is within the above range, it becomes a preferred embodiment without inhibiting bending.

Further, another example of the polarizer is a liquid crystal coated polarizer formed by applying a liquid crystal polarizing composition. The liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound. The liquid crystalline compound only needs to have a property of exhibiting a liquid crystal state, and it is particularly preferable to have a high-order alignment state such as a smectic phase because high polarizing performance can be exhibited. Moreover, the liquid crystalline compound preferably has a polymerizable functional group.
The dichroic dye compound is a dye that exhibits dichroism by aligning with the liquid crystalline compound, and may have a polymerizable functional group, and the dichroic dye itself has liquid crystallinity. You may have
Any one of the compounds contained in the liquid crystal polarizing composition has a polymerizable functional group. The liquid crystal polarizing composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent, and the like.
The liquid crystal polarizing layer is manufactured by coating a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer. The liquid crystal polarizing layer can be formed thinner than the film-type polarizer, and the thickness is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.

The alignment film is produced, for example, by coating an alignment film-forming composition on a substrate and imparting alignment properties by rubbing, polarized light irradiation, or the like. The alignment film-forming composition contains an alignment agent, and may further contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. Examples of the alignment agent include polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides. When using an alignment agent that imparts alignment properties by polarized light irradiation, it is preferable to use an alignment agent containing a cinnamate group. The weight average molecular weight of the polymer used as the alignment agent is, for example, about 10,000 to 1,000,000. The thickness of the alignment film is preferably 5 nm or more and 10,000 nm or less, and more preferably 10 nm or more and 500 nm or less in terms of sufficiently expressing the alignment control force.
The liquid crystal polarizing layer can be laminated by peeling from the base material and transferring, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a protective film, a retardation plate, or a transparent base material for a window film.

As the protective film, any transparent polymer film can be used, and the same materials and additives as those used for the transparent base material of the window film can be used. Cellulose-based films, olefin-based films, acrylic films, and polyester-based films are preferred. It may also be a coating-type protective film obtained by applying and curing a cationic curable composition such as an epoxy resin or a radical curable composition such as an acrylate. The protective film may optionally contain plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, and antioxidants. , a lubricant, a solvent, and the like. The thickness of the protective film is preferably 200 μm or less, more preferably 1 μm or more and 100 μm or less. When the thickness of the protective film is within the above range, the flexibility of the film tends to be less likely to decrease. The protective film can also serve as the transparent base material of the window film.

The λ/4 retardation plate is a film that provides a λ/4 retardation in a direction (in-plane direction of the film) perpendicular to the traveling direction of incident light. The λ/4 retardation plate may be a stretched retardation plate manufactured by stretching a polymer film such as a cellulose film, an olefin film, or a polycarbonate film. The λ / 4 retardation plate, if necessary, retardation modifiers, plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers agents, antistatic agents, antioxidants, lubricants, solvents, and the like.
The thickness of the stretched retardation plate is preferably 200 μm or less, more preferably 1 μm or more and 100 μm or less. When the thickness of the stretched retardation plate is within the above range, the flexibility of the stretched retardation plate tends to be less likely to decrease.

Another example of the λ/4 retardation plate is a liquid crystal coated retardation plate formed by coating a liquid crystal composition.
The liquid crystal composition includes a liquid crystal compound exhibiting a liquid crystal state such as nematic, cholesteric, or smectic. The liquid crystalline compound has a polymerizable functional group.
The liquid crystal composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent, and the like.
The liquid crystal-coated retardation plate can be produced by applying a liquid crystal composition on a base and curing to form a liquid crystal retardation layer in the same manner as the liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be formed thinner than the stretching type retardation plate. The thickness of the liquid crystal polarizing layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.
The liquid crystal-coated retardation plate can be laminated by peeling from the base material and transferred, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a protective film, a retardation plate, or a transparent base material for a window film.

In general, many materials exhibit larger birefringence at shorter wavelengths and smaller birefringence at longer wavelengths. In this case, it is not possible to achieve a retardation of λ/4 in the entire visible light region, so that the in-plane retardation is preferably 100 nm or more so that it is λ/4 around 560 nm where visibility is high. It is designed to be 180 nm or less, more preferably 130 nm or more and 150 nm or less. A reverse-dispersion λ/4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to that of a normal one is preferable in terms of good visibility. As such materials, for example, those described in JP-A-2007-232873 and the like for the stretched retardation plate, and those described in JP-A-2010-30979 and the like for the liquid crystal-coated retardation plate can be used. .
As another method, a technique of obtaining a broadband λ/4 retardation plate by combining with a λ/2 retardation plate is also known (for example, JP-A-10-90521). The λ/2 retardation plate is also manufactured by a material method similar to that of the λ/4 retardation plate. The combination of the stretched retardation plate and the liquid crystal-coated retardation plate is arbitrary, but the thickness of both can be reduced by using the liquid crystal-coated retardation plate.
A method is known in which a positive C plate is laminated on the circularly polarizing plate in order to improve the visibility in the oblique direction (for example, Japanese Patent Application Laid-Open No. 2014-224837). The positive C-plate may be either a liquid crystal-coated retardation plate or a stretched retardation plate. The retardation in the thickness direction of the retardation plate is preferably −200 nm or more and −20 nm or less, more preferably −140 nm or more and −40 nm or less.

(touch sensor)
A display device (preferably a flexible display device) including the laminate of the present invention preferably includes a touch sensor as described above. A touch sensor is used as an input means. As the touch sensor, there are various types such as a resistive film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and an electrostatic capacity type, and the capacitive type is preferred.
A capacitive touch sensor is divided into an active area and a non-active area located outside the active area. The active area is an area corresponding to the area (display part) where the screen is displayed on the display panel, and is an area where a user's touch is sensed. display area). The touch sensor preferably includes a flexible substrate, a sensing pattern formed in an active region of the substrate, and an external driving circuit formed in a non-active region of the substrate through the sensing pattern and a pad portion. each sensing line for connecting to a As the flexible substrate, the same material as the transparent substrate of the window film can be used. The substrate of the touch sensor preferably has a toughness of 2,000 MPa % or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness is 2,000 MPa% or more and 30,000 MPa% or less. Here, the toughness is defined as the lower area of a stress-strain curve obtained through a tensile test of a polymeric material, up to the breaking point.

The sensing patterns may include first patterns formed in a first direction and second patterns formed in a second direction. The first pattern and the second pattern are arranged in different directions. The first pattern and the second pattern are formed in the same layer, and each pattern should be electrically connected to sense a touched point. The first pattern has a form in which a plurality of unit patterns are connected to each other through joints, while the second pattern has a structure in which a plurality of unit patterns are separated from each other in an island form. A separate bridge electrode is required for direct connection. A well-known transparent electrode can be applied to the electrode for connection of the second pattern. Materials for the transparent electrode include, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), and indium gallium zinc oxide (IGZO). , cadmium tin oxide (CTO), PEDOT (poly(3,4-ethylenedioxythiophene)), carbon nanotube (CNT), graphene, metal wire, etc., preferably ITO. These can be used singly or in combination of two or more. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, terenium, chromium, etc. These may be used alone or in combination of two or more. can be done.
A bridge electrode may be formed on the insulating layer above the sensing pattern with an insulating layer interposed therebetween, and the bridge electrode may be formed on the substrate, and the insulating layer and the sensing pattern may be formed thereon. The bridge electrode may be made of the same material as the sensing pattern, and may be made of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. can.
Since the first pattern and the second pattern should be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer can be formed only between the joints of the first pattern and the bridge electrodes, or can be formed as a layer covering the entire sensing pattern. In the case of a layer covering the entire sensing pattern, the bridge electrode can connect the second pattern through contact holes formed in the insulating layer.

The touch sensor is induced by a difference in transmittance between a patterned area where a sensing pattern is formed and a non-patterned area where no sensing pattern is formed, specifically by a difference in refractive index in these areas. An optical adjustment layer may further be included between the substrate and the electrode as a means for properly compensating for differences in optical transmittance. The optical modulating layer can comprise an inorganic insulating material or an organic insulating material. The optical control layer may be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate. The photocurable composition may further include inorganic particles. The inorganic particles can increase the refractive index of the optical adjustment layer.
The photocurable organic binder includes a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, and a carboxylic acid-based monomer within a range that does not impair the effects of the present invention. be able to. The photocurable organic binder may be, for example, a copolymer containing different repeating units such as epoxy group-containing repeating units, acrylate repeating units, and carboxylic acid repeating units.
Examples of the inorganic particles include zirconia particles, titania particles, and alumina particles.
The photocurable composition may further include additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.

(adhesion layer)
Each layer (window film, circularly polarizing plate, touch sensor) forming the laminate for the display device (preferably a flexible image display device) and film members (linear polarizing plate, λ/4 retardation plate, etc.) constituting each layer are It can be joined with an adhesive. Examples of the adhesive include water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent volatile adhesives, moisture-curable adhesives, heat-curable adhesives, anaerobic-curable adhesives, and active energy ray-curable adhesives. Commonly used adhesives such as adhesives, curing agent-mixed adhesives, hot-melt adhesives, pressure-sensitive adhesives (adhesives), and rewetting adhesives can be used, preferably water-based solvent volatilization. A type adhesive, an active energy ray-curable adhesive, and a pressure-sensitive adhesive can be used. The thickness of the adhesive layer can be appropriately adjusted according to the desired adhesive strength and the like, and is preferably 0.01 to 500 μm, more preferably 0.1 to 300 μm. A plurality of adhesive layers are present in the laminate for a display device (preferably a flexible image display device), and the respective thicknesses and types may be the same or different.

As the water-based solvent volatilization adhesive, water-soluble polymers such as polyvinyl alcohol-based polymers and starch, and polymers in a water-dispersed state such as ethylene-vinyl acetate-based emulsions and styrene-butadiene-based emulsions can be used as main polymers. In addition to the main polymer and water, crosslinking agents, silane compounds, ionic compounds, crosslinking catalysts, antioxidants, dyes, pigments, inorganic fillers, organic solvents, and the like may be added. When bonding with the water-based solvent volatilization type adhesive, adhesion can be imparted by injecting the water-based solvent volatilization type adhesive between the layers to be adhered, laminating the layers to be adhered, and then drying. When the water-based solvent volatilization type adhesive is used, the thickness of the adhesive layer is preferably 0.01 to 10 μm, more preferably 0.1 to 1 μm. When the water-based solvent volatilization type adhesive is used for multiple layers, the thickness and type of each layer may be the same or different.

The active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that forms an adhesive layer upon irradiation with an active energy ray. The active energy ray-curable composition can contain at least one polymer of the same radically polymerizable compound and cationic polymerizable compound as those contained in the hard coat composition. As the radically polymerizable compound, the same compound as the radically polymerizable compound in the hard coat composition can be used.
As the cationic polymerizable compound, the same compound as the cationic polymerizable compound in the hard coat composition can be used.
Epoxy compounds are particularly preferred as the cationic polymerizable compound used in the active energy ray-curable composition. It is also preferred to contain a monofunctional compound as a reactive diluent in order to reduce the viscosity of the adhesive composition.

The active energy ray composition can contain a monofunctional compound to reduce viscosity. Examples of the monofunctional compound include acrylate-based monomers having one (meth)acryloyl group in one molecule, compounds having one epoxy group or oxetanyl group in one molecule, such as glycidyl (meth) ) acrylates and the like.
The active energy ray composition can further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., and these are appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cationic polymerization. In the description of the hard coat composition, an initiator capable of initiating at least one of radical polymerization and cationic polymerization upon exposure to active energy rays can be used.
The active energy ray-curable composition further includes an ion scavenger, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, an antifoaming agent solvent, an additive, and a solvent. can include When bonding two layers to be adhered with the active energy ray-curable adhesive, the active energy ray-curable composition is applied to one or both of the layers to be adhered, and then laminated, and any adherend layer is adhered. Alternatively, both layers to be adhered can be adhered by irradiating them with active energy rays for curing. When the active energy ray-curable adhesive is used, the adhesive layer preferably has a thickness of 0.01 to 20 μm, more preferably 0.1 to 10 μm. When the active energy ray-curable adhesive is used to form a plurality of adhesive layers, the thickness and type of each layer may be the same or different.

Any of the adhesives classified into acrylic adhesives, urethane-based adhesives, rubber-based adhesives, silicone-based adhesives, etc. can be used as the adhesive according to the main polymer. In addition to the base polymer, the adhesive may contain a cross-linking agent, a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like. An adhesive layer is formed by dissolving and dispersing each component constituting the adhesive in a solvent to obtain an adhesive composition, applying the adhesive composition on a substrate and then drying it. be. The adhesive layer may be formed directly, or may be transferred after being separately formed on the substrate. It is also preferable to use a release film to cover the adhesive surface before adhesion. When the active energy ray-curable adhesive is used, the adhesive layer preferably has a thickness of 0.1 to 500 μm, more preferably 1 to 300 μm. When using a plurality of layers of the pressure-sensitive adhesive, the thickness and type of each layer may be the same or different.

(Shading pattern)
The light shielding pattern can be applied as at least part of a bezel or housing of the display device (preferably a flexible image display device). The visibility of the image is improved by hiding the wiring arranged at the peripheral portion of the display device (preferably the flexible image display device) by the light-shielding pattern and making it difficult to see. The light shielding pattern may be in the form of a single layer or multiple layers. The color of the light-shielding pattern is not particularly limited, and various colors such as black, white, and metallic color may be used. The light-shielding pattern may be formed of pigments for realizing colors and polymers such as acryl-based resins, ester-based resins, epoxy-based resins, polyurethanes, and silicones. These may be used singly or as a mixture of two or more. The light-shielding pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern is preferably 1-100 μm, more preferably 2-50 μm. It is also preferable to impart a shape such as an inclination in the thickness direction of the light shielding pattern.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and it is of course possible to make appropriate modifications within the scope that can be adapted to the gist of the above and below. Included in scope.

[Preparation of Intermediate Layer Forming Composition]
Example 1
A reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP-A-2012-197330, represented by the following formula as an organosilicon compound (C) (trade name ;X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 0.25% by mass, 99.50% by mass of butyl acetate as solvent 1, and 0.25% by mass of acetone as solvent 2. A solution was stirred at room temperature. Then, intermediate layer-forming composition 1 was obtained.

Example 2
Intermediate layer-forming composition 2 was obtained in the same manner as in Example 1, except that 99.70% by mass of butyl acetate was used as solvent 1 and 0.05% by mass of ethanol was used as solvent 2.

Example 3
An intermediate layer was formed in the same manner as in Example 1 except that 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol was used as solvent 2. A composition 3 for

Example 4
Intermediate layer-forming composition 4 was prepared in the same manner as in Example 1 except that 99.45% by mass of butyl acetate was used as solvent 1, and 0.25% by mass of acetone and 0.05% by mass of ethanol were used as solvent 2. Obtained.

Example 5
Intermediate layer-forming composition 5 was obtained in the same manner as in Example 1, except that 97.25% by mass of butyl acetate was used as solvent 1 and 2.50% by mass of acetone was used as solvent 2.

Example 6
An intermediate layer-forming composition 6 was obtained in the same manner as in Example 1 except that 99.73% by mass of butyl acetate was used as solvent 1 and 0.025% by mass of acetone was used as solvent 2.

Example 7
Intermediate layer-forming composition 7 was obtained in the same manner as in Example 1, except that 28.50% by mass of butyl acetate was used as solvent 1 and 71.25% by mass of acetone was used as solvent 2.

Example 8
An intermediate layer-forming composition 8 was obtained in the same manner as in Example 1, except that 99.25% by mass of butyl acetate was used as solvent 1 and 0.50% by mass of diacetone alcohol was used as solvent 2.
Example 9
In the same manner as in Example 1, except that 3-(trimethoxysilyl)propan-1-amine (KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula was used as the organosilicon compound (C). An intermediate layer forming composition 9 was obtained.

Comparative example 1
A reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name: X-12- 5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) and 99.75% by mass of toluene as solvent 1 were stirred at room temperature to obtain intermediate layer forming composition 10 .

Table 1 below shows the Hansen solubility parameters and the ratio (δH/δD) of the solvent used in the composition for forming the intermediate layer, and X-12-5263HP and X-12-5263HP calculated based on the above formula (E.1). shows the distance Ra of the Hansen Solubility Parameter of .

The Hansen solubility parameters in Table 1 are for butyl acetate, toluene, acetone, ethanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol, and For acetone alcohol, the values registered in the HSPiP version 5.2.05 database are shown, and for X-12-5263HP, the values calculated by the "measurement of Hansen solubility parameter by dissolving sphere method" described later are shown. .

Measurement of Hansen solubility parameter by dissolving ball method In a transparent container, 1 mL of a solvent with known solubility parameters as shown in Table 2 (Source: Polymer Handbook 4th edition) and 1 mL of X-12-5263HP are added and the mixture is prepared. After shaking the resulting mixture, the appearance of the mixture was visually observed, and the solubility of X-12-5263HP in the solvent was evaluated based on the following evaluation criteria based on the observation results obtained. When the evaluation criterion was 1 or 2, it was determined that the solvent dissolved the measurement sample, and when the evaluation criterion was 0, it was determined that the solvent did not dissolve the measurement sample. Table 2 shows the evaluation results.
(Evaluation criteria)
2: Appearance of mixed liquid is translucent.
1: Appearance of mixed liquid is colorless and transparent.
0: The appearance of the mixed liquid is cloudy.

From the obtained solubility evaluation results, solubility spheres were created using the above-mentioned melting sphere method. The center coordinates of the resulting solubility sphere were taken as the Hansen solubility parameters of X-12-5263HP.

[Preparation of composition for forming water-repellent layer]
A compound (a10) satisfying the above formula (a3) as the organosilicon compound (A), FAS13E(C ₆ F ₁₃ —C ₂ H ₄ —Si(OC ₂ H ₅ ) ₃ as the organosilicon compound (B), Tokyo Chemical Industry Co., Ltd. Co., Ltd.) and FC-3283 (C ₉ F ₂₁ N, Fluorinert, manufactured by 3M) as solvent 4 were mixed and stirred at room temperature for a predetermined time to obtain a composition for forming a water-repellent layer. The ratio of the organosilicon compound (A) in the water-repellent layer-forming composition was 0.085% by mass, and the ratio of the organosilicon compound (B) was 0.05% by mass. The compound (a10) used as the organosilicon compound (A) is a compound that satisfies the requirements of the above-described compounds (a11) and (a21) and also satisfies the requirements of formula (a3) including preferred embodiments.

[Preparation of laminate]
Example 10
The intermediate layer-forming composition obtained above is applied onto the hard coat layer of a polyethylene terephthalate substrate having a hard coat layer whose surface to be coated is activated using an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.). 1 was applied under the conditions of 0.5 ml and 100 mm/sec using an OPTICOAT MS-A100 (bar coater) manufactured by MIKASA Co., Ltd., #2 bar, and dried at 100 ° C. for 30 seconds to form an intermediate layer. . Thereafter, the composition for forming a water-repellent layer was applied onto the intermediate layer under the same conditions as above and dried at 100° C. for 30 seconds to form a water-repellent layer.

Example 11
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, an intermediate layer-forming composition 1 subjected to an acceleration test described later was used.

40 mL of the intermediate layer-forming composition prepared for the accelerated test was placed in a disposable polypropylene container, covered with a heat-resistant gas barrier film made of polyvinylidene chloride, and then stirred at 400 rpm for 2 hours in an air atmosphere with a temperature of 22° C. and a humidity of 55%. did.

Example 12
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 2 was used instead of the intermediate layer-forming composition 1.

Example 13
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, the intermediate layer-forming composition 2 subjected to the accelerated test was used.

Example 14
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 3 was used instead of the intermediate layer-forming composition 1.

Example 15
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, the intermediate layer-forming composition 3 subjected to the accelerated test was used.

Example 16
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 4 was used instead of the intermediate layer-forming composition 1.

Example 17
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, the intermediate layer-forming composition 4 subjected to the accelerated test was used.

Example 18
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 5 was used instead of the intermediate layer-forming composition 1.

Example 19
A laminate was obtained in the same manner as in Example 10, except that instead of intermediate layer-forming composition 1, intermediate layer-forming composition 5 subjected to the accelerated test was used.

Example 20
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 6 was used instead of the intermediate layer-forming composition 1.

Example 21
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, the intermediate layer-forming composition 6 subjected to the accelerated test was used.

Example 22
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 7 was used instead of the intermediate layer-forming composition 1.

Example 23
A laminate was obtained in the same manner as in Example 10, except that instead of intermediate layer-forming composition 1, intermediate layer-forming composition 7 subjected to the accelerated test was used.

Example 24
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 8 was used instead of the intermediate layer-forming composition 1.

Example 25
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, the intermediate layer-forming composition 8 subjected to the accelerated test was used.

Example 26
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 9 was used instead of the intermediate layer-forming composition 1.

Example 27
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, the intermediate layer-forming composition 9 subjected to the accelerated test was used.

Comparative example 2
A laminate was obtained in the same manner as in Example 10, except that the intermediate layer-forming composition 10 was used instead of the intermediate layer-forming composition 1.

Comparative example 3
A laminate was obtained in the same manner as in Example 10, except that instead of the intermediate layer-forming composition 1, the intermediate layer-forming composition 10 subjected to the accelerated test was used.

The compositions and laminates obtained in the above examples and comparative examples were evaluated by the following methods. Table 3 shows the results.

Evaluation of Storage Stability Twenty-five mL of intermediate layer-forming compositions 1 to 10 were placed in 50-mL screw tubes, exposed to the atmosphere, and then stored with the lids closed. The air atmosphere had a temperature of 22° C. and a humidity of 55%. After closing the lid, the number of days until the composition became cloudy was measured. It can be said that the longer the number of days until the composition becomes cloudy, the better the storage stability of the composition.

Measurement of contact angle (initial contact angle)
A water droplet of 3 μL was dropped on the surface of the water-repellent layer side of the laminates obtained in Examples 10, 12, 14, 16, 18, 20, 22, 24, 26 and Comparative Example 2, and a contact angle measurement device ( The contact angle of water was measured by a droplet method (analysis method: θ/2 method) using DM700 manufactured by Kyowa Interface Science Co., Ltd.).

Measurement of sliding angle (initial sliding angle)
A water droplet of 6.0 μL was dropped on the surface of the water-repellent layer side of the laminates obtained in Examples 10, 12, 14, 16, 18, 20, 22, 24, and 26 and Comparative Example 2, and the contact angle Using a measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM700), the slide method (water droplet amount: 6.0 μL, tilt method: continuous slope, slide detection: after slide, slide judgment distance: 0.25 mm). The dynamic water repellency (sliding angle) of the surface of the water repellent layer (r) was measured.

Measurement of wear resistance (initial wear resistance)
The laminates obtained in Examples 10, 12, 14, 16, 18, 20, 22, 24, 26 and Comparative Example 2 were scratched using a scratching device equipped with an eraser made by Minoan. (r) A load of 1000 g is applied while in contact with the surface (contact surface: circle with a diameter of 6 mm), and the eraser is reciprocated on the laminate at a speed of 40 r / min (40 reciprocations per minute) and a stroke of 40 mm, A wear resistance test was performed. The contact angle of water was measured after the eraser reciprocated the laminate 3000 times.

Measurement of Abrasion Resistance after Acceleration Test The laminates obtained in Examples 11, 13, 15, 17, 19, 21, 23, 25 and 27 and Comparative Example 3 were scratched using a minoan eraser. , A load of 1000 g is applied with the eraser in contact with the water-repellent layer (r) surface of the laminate (contact surface: circle with a diameter of 6 mm), and the eraser is moved at a speed of 40 r / min (40 reciprocations per minute), stroke Abrasion resistance test was conducted by reciprocating on the laminate at 40 mm. The contact angle of water was measured after the eraser reciprocated the laminate 1500 times.

Visual confirmation of the surface of the coating film after the accelerated test. Check the condition of the surface. Sensory evaluation was carried out by assigning ◯ when the surface was colorless and transparent, and x when unevenness or foreign substances were observed on the surface.

Laminates having layers formed from the composition of the present invention can be used for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, window glasses for automobiles and buildings, and metals such as cooking utensils. It can be suitably used for products, ceramic products such as tableware, plastic automobile parts, etc., and is industrially useful. It is also preferably used for items such as kitchens, bathrooms, washbasins, mirrors, and members around toilets.

Claims

A mixed composition of an organosilicon compound (C) having an amino group or an amine skeleton, a solvent 1, and a solvent 2,
When the ratio of the hydrogen bonding term (δH) and the dispersion term (δD) in the Hansen solubility parameters is δH/δD, the ratio (δH/δD) of solvent 1 is less than 0.410, and the ratio of solvent 2 (δH /δD) is 0.410 or more.
The composition according to claim 1, wherein the mass ratio of solvent 2 to solvent 1 is 0.01% by mass or more and 250% by mass or less.
Solvent 2 has a Hansen solubility parameter distance Ra of 5 (J/cm 3 ) 0.5 between the solvent 2 and the non-fluorinated alcohol solvent 2-A or the organosilicon compound (C) calculated based on formula (E.1). The composition according to claim 1 or 2, comprising the following organic solvent 2-B.

[In the formula,
δD1: dispersion term (J/cm 3 ) of the Hansen solubility parameter of the organosilicon compound (C) 0.5 ,
δD2: dispersion term of Hansen solubility parameter of organic solvent 2-B (J/cm 3 ) 0.5 ,
δP1: the polar term of the Hansen solubility parameter of the organosilicon compound (C) (J/cm 3 ) 0.5 ,
δP2: Polar term of Hansen solubility parameter of organic solvent 2-B (J/cm 3 ) 0.5 ,
δH1: hydrogen bond term (J/cm 3 ) of the Hansen solubility parameter of the organosilicon compound (C) 0.5 ,
δH2: Hydrogen bond term (J/cm 3 ) of Hansen solubility parameter of organic solvent 2-B is 0.5 ]
The composition according to claim 3, wherein the solvent 2 contains a non-fluorinated alcoholic solvent 2-A and an organic solvent 2-B.
The composition according to any one of claims 1 to 4, wherein solvent 1 is an ester solvent.
The composition according to any one of claims 1 to 5, wherein a hydrolyzable group or a hydroxy group is bonded to at least one silicon atom in the organosilicon compound (C).
The composition according to any one of claims 1 to 6, wherein the organosilicon compound (C) is a compound represented by any one of formulas (c1) to (c3).

In the above formula (c1),
R x11 , R x12 , R x13 , and R x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple R x11 , the multiple R x11 may be different. may be different when there are a plurality of R x12 ; when there are a plurality of R x13 , a plurality of R x13 may be different ; may be different from each other in a plurality of R x14 ,
Rf x11 , Rf x12 , Rf x13 , and Rf x14 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf x11 are present; When there is a plurality of Rf x11, the plurality of Rf x11 may be different, when there are a plurality of Rf x12 , the plurality of Rf x12 may be different, and when there is a plurality of Rf x13 , the plurality of Rf x13 may be different. may be different, and if there are a plurality of Rf x14 , the plurality of Rf x14 may be different,
R x15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R x15 are present, the plurality of R x15 may be different,
X 11 is a hydrolyzable group, and when a plurality of X 11 are present, the plurality of X 11 may be different,
Y 11 is -NH- or -S-, and when a plurality of Y 11 are present, the plurality of Y 11 may be different,
Z 11 is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group;
p1 is an integer of 1 to 20, p2, p3, and p4 are each independently an integer of 0 to 10, p5 is an integer of 0 to 10,
p6 is an integer from 1 to 3,
has at least one Y 11 which is —NH— when Z 11 is not an amino group; when all Y 11 are —S— or when p5 is 0, Z 11 is an amino group;
Z 11 -, -Si(X 11 ) p6 (R x15 ) 3-p6 , p1 -{C(R x11 )(R x12 )}-units (U c11 ), p2 -{C(Rf x11 ) (Rf x12 )}-unit (U c12 ), p3-{Si (R x13 ) (R x14 )}-unit (U c13 ), p4-{Si (Rf x13 )(Rf x14 )} The - unit (U c14 ) and p5 -Y 11 - units (U c15 ) form one end of the compound represented by the formula (c1) where Z 11 - is, and -Si(X 11 ) p6 (R x15 ) 3-p6 is the other terminal, and the respective units (U c11 ) to (U c15 ) are aligned and bonded in any order unless —O— is linked to —O—.

In the above formula (c2),
R x20 and R x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms ; When a plurality of R x21 are present, the plurality of R x21 may be different,
Rf x20 and Rf x21 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom; x20 may be different, and when there are multiple Rf x21 , multiple Rf x21 may be different,
R x22 and R x23 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R x22 and R x23 are present, a plurality of R x22 and R x23 may be different,
X 20 and X 21 are each independently a hydrolyzable group, and when multiple X 20 and X 21 are present, multiple X 20 and X 21 may be different,
p20 is each independently an integer of 1 to 30, p21 is each independently an integer of 0 to 30, and at least one of the repeating units bracketed with p20 or p21 is an amine skeleton —NR 100 —, wherein R 100 in the amine skeleton is a hydrogen atom or an alkyl group;
p22 and p23 are each independently an integer of 1 to 3,
p20-{C( Rx20 )( Rx21 )}-units ( Uc21 ), p21-{C( Rfx20 )( Rfx21 )}-units ( Uc22 ) are p20 units ( U c21 ) or p21 units (U c22 ) do not need to be consecutive, and each unit (U c21 ) and unit (U c22 ) are lined up in any order and combined to form the formula (c2) One end of the compound is -Si(X 20 ) p22 (R x22 ) 3-p22 and the other end is -Si(X 21 ) p23 (R x23 ) 3-p23 .

In the above formula (c3),
Z 31 and Z 32 are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group,
R x31 , R x32 , R x33 , and R x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R x31 are present, the plurality of R x31 are different from each other. may be different when there are a plurality of R x32 , and when there are a plurality of R x33 , a plurality of R x33 may be different ; may be different from each other in a plurality of R x34 ,
Rf x31 , Rf x32 , Rf x33 , and Rf x34 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf x31 are present; When there is a plurality of Rf x31, the plurality of Rf x31 may be different, when there are a plurality of Rf x32 , the plurality of Rf x32 may be different, and when there is a plurality of Rf x33 , the plurality of Rf x33 may be different. may be different, and if there are a plurality of Rf x34 , the plurality of Rf x34 may be different,
Y 31 is —NH—, —N(CH 3 )— or —O—, and when there are a plurality of Y 31 , the plurality of Y 31 may be different,
X 31 , X 32 , X 33 and X 34 are each independently —OR c (R c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or aminoC 1-3 alkyldiC 1-3 alkoxysilyl is a group), and when a plurality of X 31 are present, the plurality of X 31 may be different, when a plurality of X 32 are present, the plurality of X 32 may be different, and X 33 is When a plurality of X 33 are present, the plurality of X 33 may be different, and when a plurality of X 34 are present, the plurality of X 34 may be different,
p31 is an integer of 0 to 20, p32, p33, and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, and p36 is an integer of 1 to 10 and p37 is 0 or 1,
at least one of Z 31 and Z 32 is an amino group, or at least one of Y 31 is -NH- or -N(CH 3 )-, and a compound represented by formula (c3) p31 -{C(R x31 )(R x32 )}-units, unless one end of is Z 31 - and the other end is Z 32 -, and -O- is not linked to -O- (U c31 ), p32-{C(Rf x31 )(Rf x32 )}-units (U c32 ), p33-{Si(R x33 )(R x34 )}-units (U c33 ), p34 -{Si (Rf x33 ) (Rf x34 )}-units (U c34 ), p 35 -Y 31 -units (U c35 ), p 36 -{Si (X 31 ) (X 32 )-O }-unit (U c36 ) and p37 -{Si(X 33 )(X 34 )}-units (U c37 ) are arranged in arbitrary order and bonded together.
The composition according to any one of claims 1 to 7, wherein the content of the organosilicon compound (C) is 0.005% by mass or more and 5% by mass or less.
A laminate in which a substrate (s) and a water-repellent layer (r) are laminated via an intermediate layer (c),
A laminate, wherein the intermediate layer (c) is a layer formed from the composition according to any one of claims 1 to 8.
The laminate according to claim 9, wherein the substrate (s) is a substrate composed of an organic material.
A window film or touch panel display comprising the laminate according to claim 9 or 10.